Professional Documents
Culture Documents
Conditions on
Char Properties
Bob Hawkins
Managing Research Chemist
Eprida
Athens, GA
Intro
28.50%
PN
27.50%
no steam
26.50% pine
25.50% higher temp
no vent
24.50%
vent
23.50%
0 2 4 6 8
psig
Fixed Carbon
FC%
70.00%
69.00% press
no steam
68.00%
pine
67.00%
higher temp
66.00%
no vent
65.00% vent
64.00%
0 2 4 6 8
psig
% C
55.0
60.0
65.0
70.0
75.0
80.0
PN
37
1
PN
40
2
PN
42
6
SD
37
8
SD
39
9
SD
41
8
PC
37
9
PC
40
1
PC
42
6
Carbon content
PB
38
2
PB
Charcoal sample ID
39
9
PB
42
Total Nutrients
HW 6
38
HW 2
40
HW 0
42
HR 6
38
HR 7
42
8
% N
0.00
0.50
1.00
1.50
2.00
2.50
PN
37
PN 1
40
PN 2
42
SD 6
37
SD 8
39
SD 9
41
PC 8
37
PC 9
40
PC 1
42
PB 6
Nitrogen content
38
2
PB
Charcoal sample ID
39
9
PB
42
Total Nutrients
HW 6
38
HW 2
40
HW 0
42
HR 6
38
HR 7
42
8
Total Nutrients
Al B
Ca Cu
Fe K
Mg Mn
Mo Na
P Pb
Zn
Available Nutrients
Available Potassium
1400 9000
1200 8000
7000 Pine sawdust
1000
6000 Pine chips
mg/kg
150.0 1000.0
Pine saw dust
800.0
100.0 600.0 Pine chips
m g /k g
0.00%
10.00%
20.00%
30.00%
40.00%
50.00%
0.00%
10.00%
20.00%
30.00%
40.00%
50.00%
60.00%
PN PN
37 37
1 1
PN PN
40 40
2 2
PN PN
42 42
6 6
SD SD
37 37
8 8
SD SD
39 39
9 9
SD SD
41 41
8 8
PC PC
37 37
9 9
PC PC
40 40
1 1
PC PC
42 42
6 6
PB PB
38 38
2
Available K as % of total
2
Available P as % of total
PB PB
39 39
9 9
PB PB
42 42
6 6
H
W HW
38 38
2 2
HW HW
40 40
0 0
Available Nutrients
H H
W W
42 42
6 6
H
R HR
38 38
7 7
HR H
42 R4
8 28
Char pH
Char pH
12
10
Pine sawdust
9
Pine chips
pH
8
Pine bark
7
Oak-sapwood
6
Oak-heart wood
5
360.00 370.00 380.00 390.00 400.00 410.00 420.00 430.00 440.00
Tem p
CEC
CEC
19.0
18.0
17.0
PN
16.0
15.0 +250-420
14.0 +500-850
13.0 PN-pilot
12.0
No Steam
11.0
10.0
9.0
350 400 450 500
CEC
CEC vs Pressure
14.0
12.0
10.0 PN
8.0 No Steam
6.0 Higher temp
4.0 Pine
2.0
0.0
0 2 4 6 8
Surface Acid Concentration
Charcoal surface acids (Titration w ith NaOH)
2.5
Total amount of surface acids (meq/g)
pine chips
2 Pine saw dust
Pine Bark
Hardw ood (red)
1.5
Hardw ood (w hite)
Peanut hull pellets
1 No Steam
Pilot plant
0.5
0
300 350 400 450 500
Charcoal tem perature
Char Production
Biomass in the form of mixed wood waste was pyrolysed in a fluidized bed reactor at 400, 450, 500 and
550°C. The char, liquid and gas products were analysed to determine their elemental composition
and calorific value. In particular, the liquid products were analysed in detail to determine the concentration
of environmentally hazardous polycyclic aromatic hydrocarbons (PAH) and potentially high-value
oxygenated aromatic compounds in relation to the process conditions. The gases evolved were COZ,CO and
C,-C4 hydrocarbons. The liquids were homogeneous, of low viscosity and highly oxygenated.
The molecular weight range of the liquids was 50-1300~. Chemical fractionation of the liquids showed
that only low quantities of hydrocarbons were present and the oxygenated and polar fractions were
dominant. PAH up to MW 252 were present in the liquids; some of the PAH identified have been shown to
be carcinogenic and/or mutagenic. The concentration of PAH in the liquids increased with pyrolysis
temperature, but even at the maximum pyrolysis temperature of 550°C the total concentration was
< 120ppmw. The liquids contained significant quantities of phenolic compounds and the yield of phenol
and its alkylated derivatives was highest at 500 and 550°C. Some of the oxygenated compounds identified
are of high value. Copyright 0 1996 Elsevier Science Ltd.
The energy potential of biomass and solid wastes has are often referred to as ‘flash pyrolysis’. High heating
become increasingly recognized as a means to help meet rates to temperatures > 650°C tend to favour the
world energy demand. The use of biomass has a formation of gaseous products at the expense of liquids.
particularly important role as an energy source in Slow heating rates coupled with low maximum tempera-
developing countries1’2. The utilization of biomass and tures maximize the yield of char.
other alternative fuel sources rather than existing fossil In recent years, various flash pyrolysis processes have
fuels could offer more environmentally acceptable been developed to maximize the formation of liquid
processes for energy production and will aid in conser- products for use as fuels or chemical feedstocks. A vortex
ving the limited supplies of fossil fuels. The recovery reactor process has been developed by Diebold”“. This
of energy from biomass and solid wastes has centred type of pyrolKsk process is an ablative technique. Scott
on biochemical and thermochemical processes3. Of and Piskorz ’ have designed the Waterloo flash
the thermochemical processes, pyrolysis has received pyrolysis process to maximize the liquid product yield.
increased interest, since the process conditions can be They have used small biomass particles (< 1 mm) as the
optimized to maximize the production of chars, liquids feed and high heat transfer rates with a hot fluidized bed
or gasesle3. In particular, the production of pyrolysis of sand. Georgia Tech in the USA has used an entrained
liquids has been investigated with the aim of using the flow pyrolysis reactor where the biomass particles are
liquid product directly in fuel applications or by rapidly heated by a flow of hot gases13. Vacuum pyrolysis
producing refined fuels and/or chemical has also been used as a flash pyrolysis technique by Roy
;;t;zEfj . The solid char can be used as a fuel in the et a1.14. The liquid product yields from all the above
form of briquettes or as a char-oil/water slurry, or it can processes were >50 wt%, with Dieboldgl” and Scott and
be upgraded to activated carbon and used in purification Piskorz11112reporting yields of >70 wt%.
processes”*. The gases generated have a low to medium The liquid products from flash pyrolysis processes
heating value but may contain sufficient energy to supply have been reported as being homogeneous and of
the energy requirements of a pyrolysis plant. low viscosity, and are chemically extremely complex,
The physical conditions of the pyrolysis of biomass, containing hundreds of different components’5-‘7. The
such as temperature, heating rate and residence time, chemical composition of the liquid hydrocarbons and
have been shown to have a profound effect on the the relation of composition to process conditions has
product ields and composition . High heating rates of implications for end use as a fuel or chemical feedstock.
up to lc& s-1 at temperatures < 650°C and with rapid Many biomass-derived pyrolysis oils are known to
quenching, fav&r the formation of liquid products and contain polycyclic aromatic hydrocarbons (PAH)18-20,
minimize char and gas formation; these process conditions some of which have been shown to be carcinogenic and/
n S7ktyWVe
work the pyrolysis liquids were characterized in detail in
relation to process conditions, with particular reference
II
4- to the contents of PAH and oxygenated aromatic
compounds.
EXPERIMENTAL
Biomass
The biomass used was a mixture of waste wood
shavings obtained from a woodworking company, and
therefore represented a mixture of different wood types.
Table 2 shows the proximate and ultimate analyses of the
biomass pyrolysed.
Pyrolysis reactor
The reactor system used was a fluidized bed pyrolysis
unit (Figure I). The reactor was 7.5 cm diameter x 50 cm
high, constructed from stainless steel. The fluidization
gas was nitrogen, preheated before entry into the reactor.
The flow-rate of nitrogen was sufficient to provide three
times the minimum fluidizing velocity (MFV) to the bed.
The bed material was quartz sand with a mean diameter
of 250 pm and a static bed depth of 8 cm. The biomass
was fed to the reactor via a screw feeder and nitrogen gas
stream to the top of the fluidized bed at a rate of 0.216-
0.228 kg h-l. The residence time of the pyrolytic vapours
in the hot reactor was N 2.5 s at a pyrolysis temperature
of 500°C. The pyrolysis vapours leaving the reactor were
passed through a series of condensers. The initial
Figure 1 Schematic diagram of the fluidized bed pyrolysis reactor
condensation was provided by two stainless steel
condensers which were water-cooled both internally
or mutagenic*l’**, which may have consequences for and externally, with the catch pots for each condenser
the handling of the fuel. Where the proposed end use of ice-cooled. There followed a series of glass condensers
the liquid hydrocarbons is as a chemical feedstock, again cooled using a mixture of solid carbon dioxide and
the process conditions which optimize the formation of acetone, which were used to remove any residual vapours
high-value chemicals in the liquid have economic from the gas stream. This condensation system was
benefits. In this context the oxygenated aromatic found to be 97% efficient in trapping volatile aromatic
hydrocarbons are of particular interest. Biomass-derived hydrocarbons such as toluene and 99% efficient for the
oils have been shown to contain phenols’5’23 which have condensation of water. The pyrolysis condensate from all
extensive use in the production of resins. In addition, the condensers was mixed and stored at -10°C. The
phenolic derivatives have a high value, as they are used as water fraction of the pyrolysis liquids was separated
flavourings in the food industry. Syringol and guaiacol from the organic fraction using the standard ASTM
are also found in significant concentrations in biomass- D244 and IP 29.1 methods.
derived pyrolysis oils and are used in the production of
biodegradable polyesters and polyethers. Gas analysis
In this work, a semi-continuous fluidized bed reactor
was used to flash-pyrolyse a waste wood feed. The The carrier gas stream was sampled after the
pyrolysis temperature range studied was 400-550°C as condensation system to allow for the analysis of any
this is known to give high yields of liquid products whilst non-condensable gases. Analysis was carried out using
minimizing the formation of char and gases. Pyrolytic gas chromatography. The gases determined were CO and
H2 using a molecular sieve SA 60-80 column and CO2
liquids derived from biomass have been analysed by a
using a silica column, with argon as carrier gas and
number of workers15-17, but there are limited data on the
thermal conductivity detection. For the determination of
individual yields of PAH and oxygenated aromatic
hydrocarbon gases up to Cs a Porisil C 80-100 column
compounds in relation to process conditions, coupled
with analyses of the gas phase and char. Therefore in this was used, with nitrogen as carrier gas and a flame
ionization detector.
Table 1 Proximate and ultimate analyses (wt%) of the wood feed Elemental analysis
Proximate analysis The carbon and hydrogen contents of the pyrolysis
Volatiles 91.0 liquids and char were determined using an elemental
Moisture 1.5 analyser. The oxygen content of the liquids and chars
Ash 1.5
was found by difference.
Ultimate analysis
C 45.9
H 5.12 Calor@ic value
0 46.6 The calorific value of the pyrolysis liquid was
determined by bomb calorimetry. The values reported The fractions were analysed by Fourier transform
are the gross heat of combustion at constant volume. infrared spectroscopy (FT-i.r.) to determine the efficient
separation of the chemical classes. In addition, each
Oil analysis fraction was analysed by gas chromatography-mass
Molecular weight range. The molecular weight (MW) spectrometry using ion trap detection (g.c.-ITD) to
range of the oils was determined using a mini-column verify the fractionation scheme. The percentage mass in
size exclusion chromatography (s.e.c.) system which has each class fraction was determined by analysis of the
been described previouslg4. The system incorporated two total gas chromatogram in relation to known masses of
150 mm x 4.6 mm i.d. columns with Polymer Labora- sample and standards analysed by the system. This
tories 5 pm RPSEC 100 A type packing. A third column avoided the necessity to nitrogen-evaporate (blow
of the same material was placed in line between the pump down) the solvent eluant, which may result in losses of
and the injection valve, to ensure pre-saturation of the light hydrocarbons.
solvent with the column packing material and also to
avoid analytical column dissolution and hence loss of Detailed characterization of the pyrolysis liquids. The
performance. The solvent used for the mobile phase concentrations of monocyclic and polycyclic aromatic
was tetrahydrofuran (THF), which has been shown by hydrocarbons (PAH) in the benzene fractions and the
Johnson and Chum25 to be suitable for the analysis of oxygenated aromatic species present in the ethyl acetate
biomass pyrolysis oils. The calibration system used was fraction were determined using gas chromatography-
based on polystyrene samples of low polydispersity in mass spectrometry (g.c.-m.s.) The g.c.-m.s. system
the MW range from 800 to 860000; also included was was a Carlo-Erba Vega HRGC with cold on-column
benzene for low-MW calibration. Samples were intro- injections, coupled to a Finnigan Mat ion trap detector
duced through a 2 ,ul loop injection valve. Two detectors (ITD). A DB-5 fused silica capillary column 25mx
were used: a U.V. detector sensitive to the aromatic 0.3mm was used and the temperature programme was
compounds, and a refractive index (RI) detector moni- 60°C for 2min followed by 5 Kmin-’ to 270°C with a
toring the elution of all compounds, enabling more infor- dwell time of 25 min at 270°C. The ITD mass range
mation to be obtained regarding the relative contribution was set at 30-350~ with a scan time of 0.125-2 s.
to the MW of the difference chemical class fractions24. The ITD was linked to a PC with a mass spectral library
Ultraviolet scanning of the polystyrene MW fractions facility. Identification of the individual constituents in
in THF indicated that the maximum absorbance was at the chemical fractions was carried out using the g.c.-
262nm. Determination of the maximum efficiency for m.s. and retention indices23,32Y33. Single-ion monitoring
the system showed that a mobile phase flow rate of (SIM) was also carried out to confirm the identification
0.26 mL min-’ and a column temperature between 2 of compounds and also to examine the samples for a
and 14°C were optimum24. For practical purposes the series of substituted compounds, for example, naphthalene
column was maintained at 0°C. Column temperature is and methyl-, dimethyl- and trimethylnaphthalenes.
usually maintained at room26 or elevated Quantification was determined by the use of extensive
temperature27-29. However, the optimum efficiency was external standards.
obtained at lower than ambient temperatures for the
system used in this work.
RESULTS AND DISCUSSION
Evaluation of the system has shown that there are
systematic variations in the measured MW of n-alkanes, The yields of the pyrolysis products are shown in Table 2.
n-alkenes, PAH and alkylated cyclic hydrocarbons Several repeat runs were carried out at 550°C under
compared with the polystyrene standards24. Deviations identical conditions to test the repeatability of the
from polystyrene calibration curves have also been process. The differences observed between the yields of
shown previously for other model compounds26>30>31. the char, liquid and gas for these repeat runs were
For biomass pyrolysis oils, Johnson and Chum25 used negligible. The liquid yield for all the runs was >65 wt%,
polystyrene MW fractions and showed that aromatic with a maximum yield of 67.8 wt% at 550°C. At
acids and naphthalenes deviated significantly from the pyrolysis temperatures of 500 and 550°C the pyrolysis
calibration curve. However, in this work the s.e.c. system
was used to compare oils derived from different process
conditions rather than to determine the absolute MW. Table 2 Product yields (wt%) from the flash pyrolysis of wood
liquid was a homogeneous dark liquid of low viscosity. temperatures. However, the secondary decomposition
Similar observations were made by Scott and Piskorz ’ of the char at higher temperatures may also give
using a fluidized bed process with a pyrolysis tempera- non-condensable gaseous products. Beaumont and
ture of 500°C. The pyrolytic product from the 400 and Schwob34 and Samolada et aL3’ investigated the flash
450°C fluidized bed pyrolysis temperature experiments pyrolysis of wood and found that as the pyrolysis
was found to be of low viscosity but there were traces of temperature was raised, the gaseous yield was increased.
a black tar residue on the base of the storage vial. The The yield of CO and CO2 in general increased with
pyrolysis liquid product was a mixture of organic increasing pyrolysis temperature. However, the increase
material and water. The water content of the liquid in CO was far more pronounced than that of C02. The
was determined using the ASTM D244, IP29.1 method; yield of all the hydrocarbon gases increased with
Table 3 shows the results of this separation. The water temperature. Similar observations have been made by
content of all the pyrolytic liquids was approximately other workers11’35.
the same (26.8-29.6wt%). The initial wood feed
contained 7.5 wt% moisture, which would be released Elemental analysis of pyrolysis products
during pyrolysis and subsequently collected during The liquid and char products were analysed to
condensation. This contributed approximately half determine their elemental composition. Table 5 shows
the water present in the pyrolytic liquid. Therefore the elemental compositions of the wet pyrolytic liquid,
water formed by pyrolysis accounts for 14 wt% of the the oil after removal of water, and the chars. The
liquid condensate or lOwt% of the initial wood feed. elemental compositions of the pyrolytic liquids both
Table 3 also shows that over the temperature range before and after removal of water were similar for all the
studied, the yield of oil was not significantly affected by a pyrolysis temperatures investigated. The similarity was
change in temperature. probably due to the particular temperature range
The char yield was reduced as the pyrolysis temperature studied, the lowest temperature of 400°C being adequate
was increased, from 24.1 wt% at 400°C to 16.7 wt% at to decompose the wood feed, and the low residence
550°C. The char yields reported in this work were higher time limiting the amount of secondary reactions. The
than those found by other workers1”12. This difference pyrolysis liquids arising from the reactor before water
was probably due to the fact that a mixed wood waste removal had a carbon content lower than that of the
was used in this work rather than a single known biomass initial wood feed. This indicates that such pyrolytic
feedstock as used by Scott et al.11>‘2.The decrease in the liquids have a low CV, and the removal of the water is
char yield with increasing temperature could be due necessary to maximize their CV. The composition of the
either to greater primary decomposition of the wood at pyrolytic liquid produced in this work compares well
higher temperatures or to secondary decomposition of with the finding of Churin36.
the char residue.
The gaseous product yield increased with pyrolysis Characterization of the pyrolysis liquids
temperature. The individual yields of the major gaseous Molecular weight range. The pyrolytic liquid after
species are shown in Table 4. The increase in gaseous water removal was used for determination of the MW
products is thought to be predominantly due to range of the oils, because the presence of water caused
secondary cracking of the pyrolysis vapours at higher the RI detector to give inconsistent results. Figure 2
shows MW ranges of the pyrolysis oils for the RI and
U.V. detectors. Only the data for the 400 and 550°C
Table 4 Yields (wt%) of gases from the flash pyrolysis of wood pyrolysis oils are shown, for clarity. The oils all showed
Reactor teme.
similar MW ranges from 50 to 1300~ for both the RI
(“(7 L CO COP Hz CH4 C2H6 W4 C3h C3H6
and U.V. detectors. The similarity in MW among the
oils over the temperature range studied was due to the
400 3.75 6.02 0.018 0.21 0.05 0.05 0.03 0.05 fact that the lowest temperature, 4OO”C, was sufficient
450 4.20 6.32 0.022 0.35 0.05 0.08 0.02 0.08
500 6.76 6.61 0.022 0.58 0.09 0.26 0.05 0.19 to give almost complete decomposition of the wood
550 6.71 6.86 0.023 0.69 0.16 0.26 0.04 0.45 feed and the low residence times minimized secondary
reactions which might have occurred at higher tempera-
tures. The average MW was -220 and ~275 u for the RI
Table 5 Elemental composition (wt%) of the products from the flash and U.V.detectors respectively. Diebold et a1.37 obtained
nvrolvsis of wood
flash pyrolysis oils from a vortex reactor system at
Reactor temp. (C) C H 0 625°C. They carried out s.e.c. analysis of the oil and
found components present in the oil up to and including
Total liquid product
400 38.6 8.52 51.7
2000~. Evans and Milne2’ used molecular beam mass
450 39.9 8.61 50.4 spectrometry (MB-m.s.) to analyse the pyrolysis vapours
500 37.6 8.42 53.0 whilst in the pyrolysis reactor. They found molecular
550 38.1 8.46 52.8
Liquid product after water removal
400 58.1 6.10 34.6
450 58.0 6.24 35.0 Table 6 Chemical fractionation of the pyrolysis liquids (wt%)
500 57.2 6.12 35.2
Reactor Pentane Benzene Ethyl acetate Methanol
550 59.6 6.05 33.5
temp. (“C) eluate eluate eluate eluate Total
Char
400 68.1 3.23 28.2 400 <0.2 0.42 36.2 56.8 94.6
450 71.9 3.16 24.2 450 <0.2 0.51 37.4 57.6 95.7
500 73.0 3.17 22.9 so0 <0.2 0.54 39.3 56.7 96.7
550 71.6 2.65 24.4 550 <0.2 0.54 38.4 55.2 95.3
Benzene 7 14 55 97
Toluene 5 12 35 6-l
Dimethylbenzene 1 1 2 I
Ethylbenzene 2 2 7 24
Dimethylbenzene 1 1 3 12
Trimethylbenzene 5 5 7 9
Dihydroindene <l <l <l 4
Indene 2 3 6 2
Benzofuran 1 2 4 10
0 Methylbenzofuran 3 2 5 13
1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 Tetramethylbenzene <l <l <l <l
Log Molecular Mass Methylindene <l <l <l 2
Naphthalene 3 5 4 11
(b) Methylnaphthalene 3 4 9 14
Biphenyl 1 1 1 2
Acenaphthene <l 1 1 3
Dimethylnaphthalene 3 5 9 15
Trimethylnaphthalene <l 3 5 7
Tetramethylnaphthalene <l <l <l <l
Fluorene <l <l 1 1
Methylfluorene <l <l 1 <l
Phenanthrene 3 5 6 11
Anthracene 2 2 4 6
Dimethylfluorene <l <l <l <l
Methylphenanthrene I I 10 16
Dimethylphenanthrene 3 I 8 12
Trimethylphenanthrene <l 1 1 2
b Tetramethylphenanthrene <l <l <l 2
oi,4,,,,
16 1.6 2.0
, ,
2.2 2.4
‘, ,
2.6
” ,
2.8
,
3.0
), I
3.2
Pyrene
Methylpyrene
<l
<l
<l
<l
<l
<l <l
1
dimethyl- and ethylbenzenes. The PAH found were as the liquid product from the flash pyrolysis of wood has
naphthalene and phenanthrene and their alkylated been shown to be unstable at elevated temperatures and
derivatives and in minor concentrations other compounds polymerizes when exposed to air37. The viscosity of the
such as pyrene, chrysene and benzopyrenes. The concen- pyrolytic liquid may also be increased by removing the
tration of PAH increased with increasing temperature. water, which could affect its use as a fuel.
The PAH found have been shown to be carcinogenic There are conflicting opinions as to the potential uses
and/or mutagenic2113g@. However, even at the highest of pyrolytic liquids derived from biomass. Maggi et aI.43
temperature of 550°C the total concentration of PAH state that flash pyrolysis bio-oils are corrosive, are not
quantified was < 120 ppmw. completely volatile, have a high oxygen content and do
PAH have been detected by other workers in biomass not mix readily with conventional fuels. They state
pyrolysis oils. For example, Pakdel and Roy41 analysed that bio-oils used in direct combustion processes rarely
oil from the pyrolysis of Aspen poplar wood chips in a meet the standards required for fuels. Rapper questions
vacuum pyrolysis unit. They found a wide range of PAH whether pyrolysis liquids meet the requirements of a
including naphthalene, phenanthrene and fluorene and storable liquid fuel, and states that pyrolysis oils are
their alkylated substituents, in addition to benzene and much lower in quality than even a heavy fuel oil,
its alkylated substituents. In addition, they quantified which itself has a rapidly shrinking market. However,
certain PAH, some of which were biologically active, Bridgwater45 has suggested various processes where flash
such as benzo[a]pyrene, chrysene and benzo[k]fluor- pyrolysis liquids could be used both now and in the
anthene, but were present in very low concentration, future. Many of the processes that he suggests require the
<5ppmw. However, the oil was collected at a biomass pyrolysis liquids to be refined or upgraded before they
pyrolysis temperature of only 263°C. Gasification tars, are suitable for use. Solantausta et a1.46 used flash
produced at higher temperatures (XSO’C) than the pyrolysis oils as a fuel in a diesel power plant. They
pyrolysis oils, were found to contain much higher concluded that the preliminary results were positive but
concentrations of PAH. However, the yield of gasification that further research was necessary on the storage of the
tar was small relative to that of the biomass pyrolysis oils and that the oils themselves required more detailed
oils. Elliottlg has also confirmed that PAH are not characterization. More detailed characterization of the
present in pyrolysis oils produced at temperatures pyrolysis oils is necessary to optimize their potential.
<5OO”C but markedly increase in concentration in The PAH content of any fuel is of great importance, as
gasification tars produced >7OO”C. Desbene et ~21.‘~ these compounds are environmentally hazardous and
analysed pyrolysis oils from the slow pyrolysis of therefore their concentration in a fuel should be
hornbeam biomass. The PAH detected included minimized. The process conditions used in this work
alkylated naphthalenes, biphenyls, fluorene, anthracene, show that flash pyrolysis gives only low levels of PAH
pyrene and benzofluorene. The composition of the oil formation from biomass feedstocks.
depended on whether the pyrolysis was slow or fast. The
low concentrations of PAH in the pyrolysis oils in Ethyl acetate fraction. The major compounds present
the present work are due to the process conditions used. in the ethyl acetate eluates of the pyrolysis liquids were
The relatively low temperatures and residence times identified and quantified; the results are shown in Table
restrict the formation of PAH by reducing the amount of 8. The major constituents of the eluate appear to be light
possible secondary reactions. For significant quantities organic oxygenates and phenolic material. The major
of PAH to form during the pyrolysis of biomass, long phenolic compounds present in the ethyl acetate eluate
residence times are needed at temperatures >700”C20. of the pyrolysis liquid were phenols, benzenediols, meth-
Table 7 shows that as the temperature of pyrolysis oxyphenols and dimethoxyphenols. The concentration
was increased, the concentration of PAH in the oils also of phenol and its alkylated derivatives increased as the
increased. For each individual PAH there was an increase pyrolysis temperature was increased, but 500 and
with increasing pyrolysis temperature. The reactions of 550°C gave similar yields. The formation of methoxyphe-
the pyrolysis vapours at increased temperatures result in no1 and its mono- and dimethyl derivatives was greatest
the formation of PAH. The formation of aromatic and at the lower pyrolysis temperatures. This was also true
polyaromatic hydrocarbons by secondary reactions for the overall concentration of dimethoxyphenol and
during pyrolysis has been attributed to at least two its derivatives. The more severe pyrolysis temperatures
mechanisms: a Diels-Alder type reaction, and deoxy- of 500 and 550°C would increase the possibility of
genation of oxygenated aromatic compounds42. secondary reactions that could be responsible for the
The calorific values of the pyrolysis liquid after thermal breakdown of the larger phenolic compounds
removal of water, the char and the ases from the such as methoxy- and dimethoxyphenols to phenol,
550°C run were found to be 22MJ kg- g , 25.9 MJ kg-’ which would then undergo alkylation, thus giving the
and 15.7 MJ me3 respectively. The original wood feed increase in alkylated phenols observed at 500 and 550°C.
had a CV of 17.7 MJ kg-‘. Therefore the pyrolysis liquid The ethyl acetate fraction also contained large
after removal of water contained -63% of the potential amounts of methylmethoxy-, dimethoxy-, hydroxy-
energy in the wood feed. The density of the pyrolytic methoxy- and dihydroxymethoxyphenylethanones. The
liquid (1.2 g cme3) was also much greater than that of the concentration of these compounds in the pyrolysis
initial feed (0.4 gcmp3), giving a much higher energy oils varied, depending on the pyrolysis temperature.
density. There was a significant amount of water present The other major group of compounds present in this
in the pyrolytic liquid which would significantly reduce fraction comprised cyclopentanone, cyclopentenone and
its CV. Indeed, the elemental analysis shows that the the methyl and hydroxymethyl derivatives of cyclopen-
pyrolysis liquid before removal of water contains tenone. The concentration of these compounds in the
significantly less carbon than the original biomass. pyrolysis oils increased as the pyrolysis temperature was
However, removal of the water may not be beneficial, increased. There were large amounts of light organic
compounds such as glycol aldehyde and the propyl ester production of phenolic chemical feedstocks as well as
of acetic acid, which were greatest in the pyrolysis oil for the production of liquid fuels would increase their
produced at 450°C. Other light organics present in the potential commercial exploitation. In maximizing the
oils were furanmethanol, furanone and methylfurfural. formation of individual phenolic compounds, it must be
The concentration of these compounds in general taken into account that an increase in pyrolysis
increased with pyrolysis temperature. temperature in this work tended to increase the forma-
In the work the biomass pyrolysis liquids have tion of phenol and its alkylated derivatives whilst
been shown to contain significant quantities of phenolic reducing the formation of the larger phenolic
compounds. These phenolic compounds could be compounds. Stoikos48 has reviewed the upgrading of
removed from the pyrolysis liquids prior to their biomass oils to high-value chemicals and premium-grade
combustion, as they have a significant commercial fuels. He reports that oxygenated compounds such as
value47148. The use of the pyrolysis liquids for the methylphenols (cresols), methyoxyphenol (guaiacol),
Table 8 Concentrations (ppmw) of the major constituents in the ethyl acetate eluate of the flash pyrolysis oils
MW 60 (acetic acid methyl ester or glycol aldehyde) 11876 13211 12874 12000
Acetic acid propyl ester 13214 17656 14901 15710
Cyclopentanone 2231 2310 2415 2380
Cyclopentenone 4645 4650 5315 5580
Furanmethanol 2641 2460 2412 2467
Methylcyclopentenone 610 742 898 845
Furanone 7178 8141 9542 10024
Methylfuraldehyde 0 0 0 2308
Methylcyclopentenone 0 0 0 681
Phenol 937 1073 1992 1839
Methylhydroxycyclopentenone 1987 2143 2101 2470
Methylphenol 779 1213 2215 2261
Methoxyphenol 3373 3657 2892 2930
Dimethylphenol 116 149 430 436
Methylmethoxyphenol 206 177 143 1412
Benzenediol 3432 3771 3730 4028
Methylbenzenediol 715 1313 2379 2675
Trimethylphenol 0 0 408 229
Tetramethylphenol 0 0 0 0
Dimethylmethoxyphenol 1317 1021 954 750
Hydroxymethylphenylethanone 3003 2974 2854 3097
Dimethoxyphenol 3756 3720 4120 4261
Ethenylbenzenediol n/a nla nla 1414
Methoxypropenylphenol 2711 2881 3214 3542
MW 168 (unidentified) 4271 3297 3365 3252
Methoxypropenylphenol 6645 6525 4974 4511
Hydroxymethoxyphenylethanone 1316 1723 1721 1775
Dihydroxymethoxyphenylethanone 1190 1303 1021 807
Hydroxymethoxyphenylpropanone 895 1074 876 913
MW 180 (unidentified) 3134 3017 4521 5246
Dimethoxypropenylphenol 2381 2751 2552 2257
MW 180 (unidentified) 597 703 515 465
Hydroxydimethoxybenzaldehyde 1695 1723 2195 1669
Hydroxymethoxypropenylphenol 7660 8305 8778 9203
Dimethoxypropenylphenol 5834 5520 4874 4948
Hydroxydimethoxyphenylethanone 1019 1071 1066 1026
MW210 (unidentified) 641 607 688 906
MW210 (unidentified) 1444 1861 2154 3146
Naphthol 33 40 65 54
Methylnaphthol 66 70 99 116
Dimethylnaphthol 0 0 0 0
Trimethylnaphthol 0 0 0 0
41 Pakdel, H. and Roy. C. Energy Fuels 1991,5,421 Utilisation’ (Eds A. V. Bridgwater and G. Grassi), Elsevier
42 Williams P. T. and Home, P. A. Fuel 199574, 1839 Applied Science, London, 1991, pp. 1l-92
43 Maggi, E., Grange, R. and Delmon, P. In ‘Research in Thermo- 46 Solantausta, Y., Nylund, N. O., Westerholm, M., Kolijonen, T.
chemical Biomass Conversion’ (Eds A. V. Bridgwater and and Oasmaa, A. Bioresource Technol. 1993,46, 177
J. L. Kuester), Elsevier Applied Science, London, 1988, pp. 47 Franck, H. G. and Stadelhofer, J. W. ‘Industrial Aromatic
896-910 Chemistry’, Springer-Verlag, Berlin, 1988
44 Rupp, M. In ‘Biomass Pyrolysis Liquids Upgrading and Utiliza- 48 Stoikos, T. In ‘Biomass Pyrolysis Liquids Upgrading and
tion’ (Eds A. V. Bridgwater and G. Grassi), Elsevier Applied Utilisation’ (Eds A. V. Bridgwater and G. Grassi), Elsevier
Science, London, 1991, pp. 219-225 Applied Science, London, 1991
45 Bridgwater, A. V. In ‘Biomass Pyrolysis Liquids Upgrading and
Abstract. New pyrolysis technologies have been developed that allow for carbon sequestration through
the production of sustainable energy from biomass (bioenergy). These systems produce charcoal (biochar)
and energy in the form of heat, steam, electricity, or liquid fuels. Purified hydrogen can also be produced,
allowing production of ammonia and future electric systems that utilize hydrogen (such as hydrogen fuel
cells). Pyrolysis energy systems produce more power than they consume, and can supply their own power
utilizing waste heat from the system. Therefore, this technology could be deployed without the need for
existing energy infrastructure. The biochar is a carbon-based co-product that has value as a soil
amendment, containing nutrients such as potassium (K), phosphorous (P), magnesium (Mg) and calcium
(Ca). When placed in the soil, an increase in soil organic matter (SOM) is observed, along with increases
in crop productivity, water retention, and soil biological activity as well as a decreased fertilizer
requirement. Pyrolysis technology can be deployed on a large industrial scale, or on small farm or
community scales. In these applications it can produce fuel, heat, electricity and fertilizer from crop
residues and wastes. The deployment of new biochar and bio-energy systems creates economic
opportunities for local communities through the creation of new businesses that develop to support its
infrastructure (suppliers of bio-wastes, manufacturer and distribution of co-products, and related
agricultural application services etc.). Due to its adaptability to a wide range of feedstocks, over 60
organizations are now involved in biochar research worldwide.
Biomass Transport
- manure Energy
Biofuel
- organic wastes Coproducts
bio-oil
- crop residues Industry
hydrogen
- wood waste
Pyrolysis
Residual Heat
Returned to
soil as bio-char
(Adapted from: Lehmann, J. 2007, Bioenergy in the black. Front Ecol Environ 2007; 5(7): 381–387)
Biomass Pyrolysis Technology
At the 2007 United Nations Commission on Sustainable Development, a new system of converting biomass to
energy was presented which can reduce dependence on oil. This technology is called biomass pyrolysis. In
this system, biomass is exposed to high temperatures in the absence of oxygen, producing energy and co-
products. Although pyrolysis biofuel production represents only a small portion of energy production
worldwide (UNDP 2004), it has the potential to generate electricity at a cost lower than any other biomass-to-
electricity technology available (Bridgewater et. al. 2002). A main advantage to implementing this technology
is that a pyrolysis system can supply its own power and heat by utilizing waste heat from the system, so there
is no need to supply power or heat from outside sources (Iwasaki, 2003). Therefore, these systems can be
deployed without the need for existing energy infrastructure. With these new advances, well over 15 countries
are now involved in commercializing biomass pyrolysis systems (http://terrapreta.bioenergylists.org/company).
A number of companies are working on making this technolgy more scaleable to agricultural industries with
various sizes of pyrolysis units. With these new designs, it is estimated that a 1-ton of biomass per hour unit
can produce 1 mw of electricity, 1 megawatt of usable heat and 600 pounds of charcoal per hour. A unit
capable of processing 25kg of biomass is estimated to produce 25 kw of heat and electricity and 20 pounds of
charcoal per hour.
The EPRIDA pyrolysis plant that operated at the Biomass Conversion Center in Athens, GA. until spring of 2009.
Examples of feedstocks include: coconut husks, corn stover, bean stubble, tobacco stalks, wastes from
agricultural processing, wood wastes from manufacturing and lumber industries, demolition wood wastes,
short-rotation energy crops, municipal solid waste, manure and sewage (Antal 1982). By using agricultural
wastes, biomass pyrolysis does not compete with food production.
7. Carbon from biomass pyrolysis can be used in a wide range of non-soil applications
In addition to use for soil applications, biomass carbon can also be considered for more traditional applications.
The applications for carbon and its compounds are so widespread that it would be impossible to adequately
describe them in a single article. Some common examples include: carbon black as a pigment for printing ink,
carbon paper, printer toner, a filler in plastics and rubber, graphite as a lubricant and molding material in glass
manufacture, in electrodes for dry batteries, in electroplating, in brushes for electrical motors and as a neutron
moderator in nuclear reactors. Activated carbon is used in medicine to absorb toxins, poisons or gases from the
digestive system and in air and water purification. Due to the fact the fact that carbon can form alloys with iron,
it can also be used in steel production, in chemical reduction, case hardening, and in carbides for cutting and
grinding tools. One company that has been evaluating biochar for both soil and conventional use has found that it
can become a precursor for a wide range of carbon based products (http://c6scientific.com). Another use for
biochar that can achieve carbon emission reduction credits under the Kyoto protocol is its use as a replacement
for coal in power generation. Biochar can be used as a direct replacement for coal without the need to modify
the existing powerplant. All of the CO2 that is released as a result of replacing fossil fuels with biochar counts
toward carbon emission reductions and can be traded in the carbon exchange markets. As pyrolysis systems
become more readily available, it is important that system managers take advantage of the full range of
applications and markets that may be achieved.
Conclusions
Biomass fuels such as wood, herbaceous materials and agricultural by-products currently form the world’s third
largest primary energy resource, behind coal and oil. At best, conventional biomass to energy is considered to
be carbon neutral. Harvesting biomass to produce energy may not be sustainable because it can result in reduced
soil productivity by depletion of carbon and nutrients. Biomass pyrolysis addresses this dilemma, because it can
utilize waste products and about half of the original carbon can be returned to the soil (Lehmann, 2007).
Utilizing biomass pyrolysis for the production of fuels also has significant advantages when compared to coal
fuels because it can eliminate the need for post combustion scrubbing and can reduce nitric oxide (NOx)
formation (Bisio et al., 1995). In fact such energy is actually CARBON NEGATIVE, because for each carbon
molecule recycled back to the atmosphere, one is buried in the soil, so the net effect is to reduce atmospheric
CO2!
The deployment of biomass pyrolysis systems can create new local businesses, job opportunities and raise the
income of people in rural communities (Okimori et al., 2003). Farming communities can benefit most from this
system because the biochar co-product can reduce or eliminate purchased fertilizers while sequestering
atmospheric CO2 (Glaser and others., 2002). This can create new profit centers for landowners by creating
carbon credits and energy, which farmers can use or sell. This can decentralize fertilizer and energy distribution,
making resources more available to farmers. It can reduce agricultural dependence on petroleum and natural gas
based products by allowing regional energy production that is cost competitive with fossil fuels.
Although biomass pyrolysis represents only a small portion of energy production worldwide it has the potential
to generate energy at a lower cost than other energy systems. With its carbon negative footprint, biomass
pyrolysis has the ability to do this in a way that can contribute to reduction in greenhouse gas emissions. Given
that 1) soil organic carbon is one of the largest reservoirs in interaction with the atmosphere and 2) enhancing
natural processes is thought to be the most cost-effective means of reducing atmospheric CO2; biomass
pyrolysis provides a way forward toward overcoming the obstacles that are facing biofuels production today. In
the words of USDA Soil Scientist, David Laird, we now have “A Win–Win–Win Scenario for Simultaneously
Producing Bioenergy, Permanently Sequestering Carbon, while Improving Soil and Water Quality” (Laird,
2008).
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ORIGINAL ARTICLE
Blackwell Publishing, Ltd.
Effect of charcoal
ORIGINAL ARTICLE
on N2O emissions
Abstract
Laboratory experiments were conducted to examine the effect of charcoal addition on N2O emissions
resulting from rewetting of air-dried soil. Rewetting the soil at 73% and 83% of the water-filled pore space
(WFPS) caused a N2O emission peak 6 h after the rewetting, and the cumulative N2O emissions throughout
the 120-h incubation period were 11 ± 1 and 13 ± 1 mg N m−2, respectively. However, rewetting at 64%
WFPS did not cause detectable N2O emissions (−0.016 ± 0.082 mg N m−2), suggesting a severe sensitivity to
soil moisture. When the soils were rewetted at 73% and 78% WFPS, the addition of charcoal to soil at
10 wt% supressed the N2O emissions by 89% . In contrast, the addition of the ash from the charcoal did not
suppress the N2O emissions from soil rewetted at 73% WFPS. The addition of charcoal also significantly
stimulated the N2O emissions from soil rewetted at 83% WFPS compared with the soil without charcoal
addition (P < 0.01). Moreover, the addition of KCl and K2SO4 did not show a clear difference in the N2O
emission pattern, although Cl− and SO4 , which were the major anions in the charcoal, had different
2−
effects on N2O-reducing activity. These results indicate that the suppression of N2O emissions by the
addition of charcoal may not result in stimulation of the N2O-reducing activity in the soil because of
changes in soil chemical properties.
Key words: denitrification, K fertilization, liming, N2O-reducing activity, rewetting effect.
(e.g. Kusa et al. 2006; Ruser et al. 2001) and have been pH (H2O) value was determined in a 1:2.5 air-dried soil
reproduced in laboratory incubation experiments as a (weight) to deionized water (volume) ratio. Total carbon
rewetting of dry soil (Rudaz et al. 1991). Rudaz et al. and nitrogen contents of the soils were determined
(1991) and Ruser et al. (2006) investigated the contri- using the dry combustion method using a CN CORDER
bution of nitrification and denitrification to the produc- MT-700 (Yanaco, Kyoto, Japan). Water soluble organic C
−
tion of N2O emitted after rewetting using the C2H2 and NO3-N contents were determined using a TOC
addition method and 15N tracing technique, respectively, meter (TOC-VCSH, SHIMADZU Co. Ltd., Kyoto, Japan)
and concluded that the N2O was mainly produced and an ion chromatograph (LC-20AT, SHIMADZU Co.
through denitrification. In the present study, to examine Ltd., Kyoto, Japan), respectively, in 1:10 extracts (air-dried
the relationship between enhancing the N2O-reducing soil to deionized water w/v) at 240 rpm for 30 min. The
activity of denitrifying communities and N2O emissions population density of denitrifiers in the air-dried soil
from soil, we examined the effects of charcoal and samples was determined using the most probable number
anion species on N2O emissions caused by the rewetting method in five replicates of 10-fold serial dilution (Tiedje
of air-dried soil in the laboratory. 1994). Maximum water-holding capacity (MWHC) was
determined using the Hilgard method. Particle density
was determined using the pycnometer method (Blake
MATERIALS AND METHODS and Hartge 1986). Water-filled pore space (WFPS) was
calculated as follows:
Soil samples and charcoal
WFPS = (Gravimetric water content/ρH2O) ·
The soil samples examined were the same as those used
(Bulk density/Porosity)
in our previous study (Yanai et al.). Soil sampling was
conducted at the Field Museum Tsukui, the Field where Porosity = 1 − (Bulk density/Particle density). In the
Science Center of Tokyo University of Agriculture and present study, we set the density of water (ρH2O) at 1 g cm−3.
Technology, Tokyo, Japan. Soil samples were collected The charcoal, which was made from municipal biowaste,
from a grassland field in which one side was planted was provided by JFE Holdings. The physico-chemical
with Sorghum bicolor (L.) Moench and the other with properties of the charcoal are listed in Yanai et al. and
Sorghum sudanense (Piper) on April 2004 and March its potential usefulness for cultivation was demonstrated
2005, respectively. The soil is classified as Typic by Nerome et al. (2005). Some selected physico-chemical
Hapludand, and the soil texture is loam to clay loam at properties of the charcoal and its ash, which was obtained
a depth of 0–40 cm, with a granular structure (Kurokawa, by heating at 700°C for 4 h (as the test of weight loss-on-
pers. comm.). After collection, moist soil samples were ignition; LOI), are listed in Table 2. Charcoal and ash
passed through a 2-mm mesh sieve, and part of the pH (H2O) values were determined in a 1:5 air-dried
sample was then air-dried. Selected physico-chemical material to deionized water ratio (w/v). The MWHC and
properties of the soil samples are listed in Table 1. Soil particle density were determined as described above. Anion
Table 1 Selected physico-chemical properties of the air-dried soils examined in this study (oven-dry basis)
TG2004 Apr. 2004 6.0 69.6 5.62 12.4 155 45.8 6.5 0.15 1.21 0.58 2.05 0.72
TG2005 Mar. 2005 5.4 70.3 5.45 12.9 74 6.4 6.2 0.13 1.11 0.59 2.03 0.71
MPN, most probable number; MWHC, maximum water-holding capacity; WSOC, water soluble organic carbon.
Table 2 Selected physico-chemical properties of charcoal and its ash examined in this study
Anion content
Water Bulk Particle
(µmol g−1)‡
pH LOI content MWHC density density
−
(H2O)† (%) (g H2O g−1) (g H2O g−1) (g cm−3) (g cm−3) Cl− NO3 SO4
2−
−
contents (Cl−, NO3 and SO4 ) in these materials were
2−
soil samples at 17.0, 19.9 and 23.1 mL to adjust the
determined using an ion chromatograph (LC-20AT, rewetted condition to 70, 80 and 91% MWHC, equivalent
SHIMADZU Co. Ltd. Kyoto, Japan) in 1:20 extracts to 64, 73 and 83% WFPS, respectively. This experiment
(air-dried material to deionized water w/v) at 240 rpm was conducted in triplicate.
for 30 min.
Effect of soil amendments on N2O emissions
Measurement of N2O emissions from soil from soil resulting from rewetting
after rewetting Based on the result of the preliminary experiment (Fig. 1),
To simulate the thin surface layer in arable fields, where the moisture content after rewetting was adjusted to
the soil could be subjected to air-drying following more than 73% WFPS in this study. First, to simulate
continuous clear weather, 30 g of sieved air-dried soil precipitation in grassland amended with charcoal in the
was placed in a Petri dish (1.3 cm height and 8.5 cm surface layer, 2 mm-sieved charcoal was mixed with
diameter) without compaction. As a result, the thickness soil (TG2004) in three of six Petri dishes at 10 wt%
of the soil was approximately 0.8 cm. To simulate the (equivalent to 13 vol%) before rewetting, and the N2O
condition of the soil during or immediately after precip- emissions were compared with the remaining three Petri
itation, distilled water was added into the soil samples dishes as the non-added control. The soil samples were
in the Petri dishes to more than 70% of their MWHC added with distilled water to moisten the soil of the
(equivalent to 64% of the water-filled pore space [WFPS]). non-added control at 78% WFPS. Second, to test whether
Immediately after rewetting the soil sample, N2O the effect of the charcoal addition on the N2O emission
emissions were periodically measured using the closed- results from the stimulation of N2O-reducing activity by
chamber method (Hutchinson and Mosier 1981). A pH increase, the charcoal or its ash was mixed with soil
clear glass bell-jar (14 cm width, 26 cm height, 2.32 L) (TG2005) in three of nine Petri dishes before rewetting,
was used as a gas-tight chamber to monitor the concen- and three Petri dishes as the non-added control. The
tration change in the headspace gas. The inlet and outlet amounts of added charcoal and its ash were determined
of the bell-jar were sealed with a rubber stopper and a in order to set soil pH (H2O) at 6.0, and the rate of
rubber septum, respectively, and the bottom part of the addition was 8.2 and 1.6 wt%, equivalent to 9.7 and
bell-jar was tightly attached with a ground glass-plate 2.0 vol%, respectively. The soil samples were rewetted
using a high vacuum-sealing compound (HIVAC-G, by adding distilled water, which was necessary to
Shin-Etsu Chemical Co. Ltd., Tokyo, Japan). A pressure-
controlling bent (Hutchinson and Mosier 1981) was
installed at the rubber stopper in the inlet and gas samples
were collected through the rubber septum installed at the
outlet. After placing the chamber onto the soil sample,
headspace gas was withdrawn five times at 2 or 8 min
intervals, depending on the rate of concentration change.
N2O concentration in the collected gas sample was analyzed
using a gas chromatograph (GC-14A, SHIMADZU,
Kyoto, Japan) equipped with an electron capture detector
and a stainless steel column packed with Porapak-Q (80/
100 mesh, 3 mm diameter, 2 m length). The column and
detector temperatures were kept at 90°C and 330°C,
respectively. Argon containing 5% CH4 was used as a
carrier gas at a flow rate of 23 mL min−1. The N2O emis-
sion rate was calculated using the linear regression method
(Hutchinson and Mosier 1981). After measurement of
the N2O emission rate, the chamber was removed and the
soil sample was left at room temperature (approximately Figure 1 Effect of rewetting on N2O emissions from soil
20–28°C) without a lid on the Petri dish. The water (TG2005). An air-dried soil sample was rewetted using
content was maintained during the incubation period distilled water at 64 (×), 73 () and 83% () of the water-filled
by adding distilled water. N2O emissions were monitored pore space (WFPS) and incubated at room temperature. The
values shown are the mean ± standard deviation of three replicates.
until the first peak of N2O emissions disappeared.
The cumulative N2O emissions during the 120-h incubation
As a preliminary experiment, we examined the effect period at a rewetting level of 64, 73 and 83% WFPS were
of moisture content after rewetting on the N2O emissions −0.016 ± 0.082, 11 ± 1 and 13 ± 1 mg N m−2 (equivalent to
from soil (TG2005). Distilled water was added into the −0.003 ± 0.03, 2.3 ± 0.3 and 2.8 ± 0.4 µg N g−1soil), respectively.
moisten the soil of the non-added control at 73% WFPS. 83% WFPS, and the cumulative N2O emissions throughout
Third, to estimate the interaction between the rate of the 120-h incubation period at room temperature
charcoal addition and the moisture content after rewet- were −0.016 ± 0.082, 11 ± 1 and 13 ± 1 mg N2O-N m−2
ting, N2O emissions were compared with three levels of (−0.003 ± 0.03, 2.3 ± 0.3 and 2.8 ± 0.4 µg N2O-N g−1soil),
charcoal additions (0, 2 and 8.2 wt%, equivalent to 0, respectively (Fig. 1). Rewetting over 73% WFPS triggered
2.4 and 9.7 vol%, respectively) in triplicate. Distilled N2O emissions, but there were no significant differences
water was added to the soil samples to moisten the soil in the cumulative N2O emissions between soils rewetted
of the non-added control (0% charcoal) at 83% WFPS. at 73% and 83% WFPS (P = 0.180).
Finally, as Cl− and SO2− 4
were not only the major anion
species of the charcoal (Table 2), but also were applied Effects of charcoal addition on N2O emissions
into arable fields through fertilization, we examined the after rewetting at 73% WFPS for TG2004
effect of anion species of K solution on N2O emissions The highest N2O emission rate was observed 30 h
after rewetting. Of the nine Petri dishes containing the after rewetting, and the values were 2620 ± 460 and
soil samples (TG2005), distilled water, 10 mmol L−1 KCl 383 ± 74 µg N m−2 h−1 in the treatments without and with
and 5 mmol L−1 K2SO4 solution were each added to three charcoal addition, respectively (Fig. 2). The addition of
dishes to adjust to 73% WFPS of the soil, and the N2O
emissions were compared. The concentration of K solution
was decided based on the concentration of K in a commer-
cial liquid fertilizer (Otsuka Chemical Co. Ltd., Osaka,
Japan), and the estimated load of Cl− and SO4 added with
2−
Table 3 Estimation of Cl− and SO4 load onto soil (TG2005) by the addition of charcoal, ash and K solution
2−
NA, not applicable with respect to the objectives of this study; WFPS, water-filled pore space.
Although there was no direct evidence to show a nium and nitrate nitrogen. J. Plant Nutr. Soil Sci., 166,
linkage between the addition of charcoal and the 594 –600.
suppression of N2O emissions from soil (Figs 2,3), the Blake GR, Hartge KH 1986: Particle density. In Physical and
added charcoal itself probably absorbed water and Mineralogical Methods. Ed. A Klute, pp. 377–382, Soil
Science Society of America, Madison.
improved the aeration of the soil, leading to a suppression
− − Bland M, Peacock J 2002: Normal distribution. In Statistical
of N2O production (stepwise reduction of NO3 , NO2
Questions in Evidence-based Medicine. Ed. K Adachi, pp.
and NO) similar to the soil rewetted at 64% WFPS (Fig. 1). 79–85, Shinoharashinsha Press, Tokyo (in Japanese).
In fact, the charcoal examined was made up of porous Borken W, Brumme R 1997: Liming practice in temperate
particles, whereas the ash was nearly pulverized. Such forest ecosystems and the effects on CO 2, N2O and CH4
differences in the size and structure possibly affect the water fluxes. Soil Use Manage., 13, 251–257.
absorption capacity of these materials, and may conse- Borken W, Grundel S, Beese F 2000: Potential contribution of
quently cause differences in the soil aeration, the denitrifi- Lumbricus terrestris L. to carbon dioxide, methane and
cation process, and N2O emissions from soil, although nitrous oxide fluxes from a forest soil. Biol. Fertil. Soils,
the charcoal addition did not significantly affect the 32, 142–148.
MWHC or the particle density (data not shown). Hence, Bouwman AF 1990: Exchange of greenhouse gases between
terrestrial ecosystems and the atmosphere. In Soils and
the significant increases in N2O emissions by the addi-
the Greenhouse Effect. Ed. AF Bouwman, pp. 61–127.
tion of charcoal to soil rewetted at 83% WFPS (Fig. 4)
John Wiley, New York.
can be interpreted as an interaction between the insig- Butterbach-Bahl K, Gasche R, Breuer L, Papen H 1997: Fluxes
nificant improvement of the aeration of the soil and the of NO and N2O from temperate forest soils: Impact of
stimulation of the N2O-producing activity resulting forest type, N deposition and of liming on the NO and
from neutralization (e.g. Cavigelli and Robertson 2000). N2O emissions. Nutr. Cycl. Agroecosys., 48, 79–90.
Charcoal was examined in this study because of its Cavigelli MA, Robertson GP 2000: The functional significance
potential use for soil amendments in temperate regions of denitrifier community composition in a terrestrial
(Nerome et al. 2005) and in the tropics (Glaser et al. 2002; ecosystem. Ecology, 81, 1402–1414.
Yamato et al. 2006). Although any extrapolation of the Cavigelli MA, Robertson GP 2001: Role of denitrifier diversity
findings from this short-term laboratory study to a long- in rates of nitrous oxide consumption in a terrestrial
ecosystem. Soil Biol. Biochem., 33, 297–310.
term field scale should be conducted with caution, field
Clough TJ, Kelliher FM, Sherlock RR, Ford CD 2004: Lime
applications of charcoal possibly suppress N2O emissions
and soil moisture effects on nitrous oxide emissions from
from arable soil, depending on the moisture or aeration a urine patch. Soil Sci. Soc. Am. J., 68, 1600–1609.
conditions of the soil. In contrast, our understanding of the Clough TJ, Sherlock RR, Kelliher FM 2003: Can liming
process of suppressing N2O emissions from soil by charcoal is mitigate N2O fluxes from a urine-amended soil? Aust. J.
still preliminary. Therefore, further studies are necessary to Soil Res., 41, 439–457.
understand both the mechanisms and possible side-effects Crutzen PJ 1981: Atmospheric chemical processes of the oxides
of charcoal addition to soil on the suppression of N2O of nitrogen, including nitrous oxide. In Denitrification,
−
emissions from soil, such as the activity of NO3 assimila- Nitrification and Atmospheric Nitrous Oxide. Ed. CC
− Delwiche, pp. 17– 44. John Wiley, New York.
tion, NO2 accumulation in soil or NOx emissions from soil.
Glaser B, Lehmann J, Zech W 2002: Ameliorating physical
and chemical properties of highly weathered soils in the
ACKNOWLEDGMENTS tropics with charcoal – A review. Biol. Fertil. Soils, 35,
219–230.
The authors thank Dr Yuzo Kurokawa (Tokyo University Hutchinson GL, Mosier AR 1981: Improved soil cover
of Agriculture and Technology) for providing soil samples method for field measurement of nitrous oxide fluxes.
and Mr Sumio Yamada (JFE Holdings) for providing the Soil Sci. Soc. Am. J., 45, 311–316.
charcoal samples. The work described in this report was Inubushi K, Barahona MA, Yamakawa K 1999: Effects of
financially supported by a Sasakawa Scientific Research salts and moisture content on nitrous oxide emission and
Grant from The Japan Science Society (16-315), the TUA&T nitrogen dynamics in Yellow soil and Andosol in model
21 Century COE program (Evolution and Survival of experiments. Biol. Fertil. Soils, 29, 401– 407.
Technology-based Civilization: Professor Masayuki Horio) Khalil MI, Van Cleemput O, Rosenani AB, Fauziah CI,
and by the Japan Society for the Promotion of Science Shamshuddin J 2003: Nitrous oxide formation potential
of various humid tropic soils of Malaysia: A laboratory
Research Fellowships for Young Scientists (17-6518).
study. Nutr. Cycl. Agroecosys., 66, 13–21.
Klemedtsson L, Klemedtsson AK, Moldan F, Weslien P 1997:
Nitrous oxide emission from Swedish forest soils in
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relation to liming and simulated increased N-deposition.
Azam F, Müller C 2003: Effect of sodium chloride on deni- Biol. Fertil. Soils, 25, 290–295.
trification in glucose amended soil treated with ammo- Kusa K, Hu R, Sawamoto T, Hatano R 2006: Three years of
nitrous oxide and nitric oxide emissions from silandic Biochemical Properties. Eds RD Weaver, JS Angle and PS
andosols cultivated with maize in Hokkaido, Japan. Soil Bottomley, pp. 245–267, Soil Science Society of America,
Sci. Plant Nutr., 52, 103 –113. Madison.
Mosier AR, Delgado JA, Keller M 1998: Methane and nitrous Tokuda S, Hayatsu M 2004: Nitrous oxide flux from a tea
oxide fluxes in an acid Oxisol in western Puerto Rico: field amended with a large amount of nitrogen fertilizer
Effects of tillage, liming and fertilization. Soil Biol. and soil environmental factors controlling the flux. Soil
Biochem., 30, 2087–2098. Sci. Plant Nutr., 50, 365–374.
Nerome M, Toyota K, Islam T-MD et al. 2005: Suppression Wang YP, Meyer CP, Galbally IE, Smith CJ 1997: Compari-
of bacterial wilt of tomato by incorporation of municipal sons of field measurements of carbon dioxide and
biowaste charcoal into soil. Soil Microorganisms, 59, nitrous oxide fluxes with model simulations for a legume
9–14 (in Japanese with English summary). pasture in southeast Australia. J. Geophys. Res., 102,
Rudaz AO, Davidson EA, Firestone MK 1991: Sources of 28 013–28 024.
nitrous oxide production following wetting of dry soil. Yamato M, Okimori Y, Wibowo IF, Anshori S, Ogawa M
FEMS Microbiol. Ecol., 85, 117–124. 2006: Effects of the application of charred bark of Acacia
Ruser R, Flessa H, Russow R, Schmidt G, Buegger F, Munch mangium on the yield of maize, cowpea and peanut, and
JC 2006: Emission of N2O, N2 and CO2 from soil ferti- soil chemical properties in South Sumatra, Indonesia. Soil
lized with nitrate: Effect of compaction, soil moisture and Sci. Plant Nutr., 52, 489– 495.
rewetting. Soil Biol. Biochem., 38, 263–274. Yanai Y, Hatano R, Okazaki M, Toyota K. Chemical factors
Ruser R, Flessa H, Schilling R, Beese F, Munch JC 2001: affecting the N2O-reducing activity of denitrifying com-
Effect of crop type-specific soil management and N munities – Analysis of the C2H2 inhibition-based N2O
fertilization on N2O emissions from a fine-loamy soil. production curve of soil.
Nutr. Cycl. Agroecosys., 59, 177–191. Zumft WG 1997: Cell biology and molecular basis of denitri-
Tiedje JM 1994: Denitrifiers. In Microbiological and fication. Microbiol. Mol. Biol. Rev., 61, 533–616.
Afforestation &
Demand-side EE Reforestation
1% 0.4%
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
$ = CO2 Sequestered x Price
• Low Quality US Projects
• Chicago Climate Exchange: $2-$4/mt CO2
• High Quality US Projects
• Voluntary Carbon Standard: $4-$9/mt CO2
• California Climate Action Registry: $5-$11/mt CO2
• Mature International Markets
• EU Emissions Trading Scheme: $10-$40/mt CO2
• Projections for Early US Market
• Markey-Waxman Bill : $10-$15/mt CO2
Biochar GHG Reductions
GHG Reduction Reduction Size Qualify for Carbon
Finance?
Sequestration Large Yes
• Small scale
• No credit for carbon sequestration, but…
• Char must be “biologically inert”
• Volatile C/Fixed C ratio lower than 50%
Next Step: Sequestered Carbon
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
Unresolved Methodology
Issues
• Recalcitrance
• Guarantee 100 years of permanent
sequestration
• Carbon Gold: Volatile C/Fixed C ratio
lower than 50%
• Soil monitoring
• What happens to char that erodes out of
the soils?
Unresolved Methodology
Issues
• Ownership – Three entities, same reduction
1. Feedstock owner
2. Pyrolysis plant
3. Land owner
Peter Weisberg
Offset Project Analyst
pweisberg@climatetrust.org
503-238-1915
Outline
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
Source: The McKinsey Quarterly. 2007. “A cost curve for greenhouse gas reductions.”
US Offset Market
• Trends
– Fossil fuels will likely be capped
– Favor domestic projects over international projects
Afforestation &
Demand-side EE Reforestation
1% 0.4%
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
$ = CO2 Sequestered x Price
• Low Quality US Projects
• Chicago Climate Exchange: $2-$4/mt CO2
• High Quality US Projects
• Voluntary Carbon Standard: $4-$9/mt CO2
• California Climate Action Registry: $5-$11/mt CO2
• Mature International Markets
• EU Emissions Trading Scheme: $10-$40/mt CO2
• Projections for Early US Market
• Markey-Waxman Bill : $10-$15/mt CO2
Biochar GHG Reductions
GHG Reduction Reduction Size Qualify for Carbon
Finance?
Sequestration Large Yes
• Small scale
• No credit for carbon sequestration, but…
• Char must be “biologically inert”
• Volatile C/Fixed C ratio lower than 50%
Next Step: Sequestered Carbon
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
Unresolved Methodology
Issues
• Recalcitrance
• Guarantee 100 years of permanent
sequestration
• Carbon Gold: Volatile C/Fixed C ratio
lower than 50%
• Soil monitoring
• What happens to char that erodes out of
the soils?
Unresolved Methodology
Issues
• Ownership – Three entities, same reduction
1. Feedstock owner
2. Pyrolysis plant
3. Land owner
• Theory of offsets
• How offsets could support biochar projects
• Methodology issues
• Current funding from The Climate Trust
• 3 Programs
• Oregon Program
• Smart Energy
• Colorado Carbon Fund
Upfront Payment
Annual
Contract
Proposal Due Commercial Monitoring
Negotiation
Diligence Operation
Annual payment
“upon delivery”
Peter Weisberg
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pweisberg@climatetrust.org
503-238-1915 x 207
Chemosphere 67 (2007) 1033–1042
www.elsevier.com/locate/chemosphere
a
CSIRO Land and Water, Adelaide Laboratory, Waite Road, Urrbrae SA, Australia
b
Institute of Crop Science and Resource Conservation of the University of Bonn, Division of Soil Science, Nussallee 13, 53115 Bonn, Germany
Received 27 June 2006; received in revised form 13 October 2006; accepted 19 October 2006
Available online 8 December 2006
In memory of the 100th anniversary of the birth of Prof. Dr. H.C. Eduard Mückenhausen (February 17th 1907)
Abstract
Naturally occurring charcoals are increasingly being recognized as effective sorbents for organic compounds. In this study we inves-
tigated the sorption of benzene and toluene in single-sorbate and bi-sorbate systems on different types of charcoals produced in labora-
tory, employing the batch sorption technique. Air dried plant materials from Phalaris grass (Phalaris tuberosa) and Red Gum wood
(Eucalyptus camadulensis) were combusted under limited oxygen supply at 250 C, 450 C, and 850 C. The resulting charcoals were char-
acterized for their specific surface areas, total cation content, and pore size distributions (pore size distribution only for wood combusted
at 450 C and 850 C). For the materials treated at 850 C not only the surface area, microporosity, and total amount of sorbed sorbate
increased markedly, but also the non-linearity of the sorption isotherm. The pore size distributions and surface areas as well as an indif-
ferent sorption behaviour and competition effects for both sorbates indicated that pore filling mechanisms were the dominating processes
governing the sorption on these microporous, high temperature treated materials. For the materials treated at lower temperatures the
affinity of toluene was higher compared to that of benzene. In the bi-sorbate system the overall uptake of benzene increased. These phe-
nomena might be due to the stronger hydrophobicity of toluene, and to a varying potential for swelling of the matrix and pore defor-
mation by the two sorbates. The significantly lower sorption capacity of the Phalaris-derived material compared to the Red Gum
charcoal correlated with its smaller surface area and higher cation content.
2006 Elsevier Ltd. All rights reserved.
0045-6535/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2006.10.052
1034 L.C. Bornemann et al. / Chemosphere 67 (2007) 1033–1042
(PCDD) have been detected on carbonaceous geosorbents land wildfires ranging up to levels between 700 C and
and are contaminants of environmental concern (e.g. 1000 C. Despite these extreme temperature ranges, artifi-
Accardi-Dey and Gschwend, 2003; Abelmann et al., cial charcoals as used in most sorption studies consisted
2005; Lohmann et al., 2005). However, the majority of either of charcoals produced from one fixed, or only a
studies dealing with sorption on activated carbon, soot, small range of temperatures (Sander and Pignatello,
coal, charcoal, graphite, opaque particles and other forms 2005; Zhu and Pignatello, 2005; Zhu et al., 2005). A study
of BC has been conducted utilizing rather simple aromatic by James et al. (2005), however, employed a range of differ-
compounds as model substances like benzene, toluene, or ent combustion temperatures for three species of softwood.
phenanthrene (e.g. Gustafsson et al., 1997; Kleineidam Still, the sorptive behaviour of the range of natural char-
et al., 2002; Zhu and Pignatello, 2005). The sorption of coals remains poorly understood and data is lacking for
these model substances on BC species has been shown to charcoals produced from different parent materials at var-
be strong and highly non-linear (e.g. Accardi-Dey and ious temperatures.
Gschwend, 2003; Braida et al., 2003; Nguyen et al., 2004; The objectives of this study were (i) investigate the sorp-
James et al., 2005). Several attempts to explain the sorption tive properties of charcoals produced from hardwood and
behaviour of organic materials with varying physicochem- herbaceous material at various temperatures representative
ical properties have been made during the last decade. of wildfires, and (ii) compare the sorption behaviour of two
Chiou et al. (2000) introduced the term of ‘‘high surface simple aromatic model compounds on the range of char-
area carbonaceous material’’ (HSACM). Small amounts coals in single and bi-sorbate systems.
of charred material like soot or charcoal are considered
to be responsible for the non-linear sorption of polar and 2. Experimental section
apolar components. The involved mechanisms are assumed
to be hydrophobic partitioning and pore filling, according 2.1. Wood and grass charcoal production
to the Polanyi–Manes (PM) model (Manes, 1998). The the-
ory postulates the existence of a nonpolar, microporous Red Gum (Eucalyptus camadulensis) chips, as used for
adsorption site with a characteristic adsorption potential, gardening purposes, were purchased from a landscape sup-
which is influenced by the nature of the sorbent, and the plier, and a pure stand of Phalaris pasture grass (Phalaris
distance of the sorption site from the sorbent surface. Also tuberosa) was cut from a meadow. Both materials were
interactions of water and adsorbent surface are taken into air dried at 40 C. Thin pieces of Red Gum wood were
account. The fundamental idea is a condensation of the hand picked, the Phalaris grass was milled into coarse seg-
adsorbate in (micro-) pores while exhibiting the same phys- ments and the dust was separated by sieving (2 mm grid).
ical properties as the unconfined bulk organic liquid or To allow a uniform combustion process, the materials were
solid. The sorption capacity is believed to be restricted by stacked uncongested in porcelain crucibles with lids. The
the pore volume occupied by the mixed phase of condensed filled crucibles were weighed and subsequently placed in a
liquids or solids. Consequently, the sorption of hydropho- muffle furnace. For the charcoals combusted at 250 C
bic organic contaminants (HOC) on BC materials would be and 450 C, the furnace was ramped from room tempera-
mainly governed by its microporosity and its hydrophobic ture to the final temperature in 1 h. As a second stage,
character. the final temperature was held for 2 h for the Red Gum
The physical properties of charcoals from burned bio- wood. Due to the more combustible nature of the Phalaris
mass are strongly dependent on the conditions during the grass, the final temperature was held only for 1 h in this
combustion process (Shafizadeh, 1984). According to case. The furnace was then switched off to allow the cruci-
Schmidt and Noack (2000), charcoals produced by vegeta- bles to cool down to room temperature. The Red Gum
tion wildfires consist mainly of several randomly orientated wood treated at 850 C was combusted for only 1 h after
stacks of graphitic sheets. Still, the structure is influenced reaching the final temperature, for the Phalaris grass the
crucially by a number of combustion parameters. The main time was reduced to half an hour. The charred material
factors are the fuel type, fuel load, fuel condition, weather was weighed and grinded to powder on a N.V. THEMA
condition, substrate heterogeneity, fire intensity, and dura- disc-rotating mill for 3 min. In the following, the abbrevia-
tion (Patterson et al., 1987). Karapanagioti et al. (2004) tions R250, R450, and R850 are used for the Red Gum
stated that ‘‘. . .the charcoal particle subgroup of organic charcoals, P250, P450 and P850 for the Phalaris charcoals.
matter is heterogeneous in nature’’, and therefore con-
cluded that different subgroups of charcoal have to be dis- 2.2. Determination of charcoal properties
tinguished in order to optimize the predictions for the bulk
sorption behaviour. The continuous flow method at 77 K was employed for
So far, little attention has been directed to the heteroge- quantification of adsorbed and desorbed N2, using a
neity within the subgroup of charcoals. From work of Rai- QUANTACHROME QUANTASORB QS-13 Surface-
son (1979) and Scott (1989) we know that elevated ground Area Particle-Size Analyzer and ultra high purity gaseous
temperatures during most wildfires may vary between nitrogen (99.999%, from BOC Gases). Surface areas for
200 C and 500 C, with highest temperatures for scrub- all six utilized charcoals were calculated from three-point
L.C. Bornemann et al. / Chemosphere 67 (2007) 1033–1042 1035
N2 BET-SSAe
R850 was evaluated using BET nitrogen adsorption tech-
nique at 77 K. The details of the method and uncertainties
(m2 g 1)
associated with the measurement have been published
605
371
34
20
8
4
elsewhere (Badalyan and Pendleton, 2003). Outgassing of
the charcoal was carried out at 300 C for 8 h at a back-
ground vacuum of 1 · 10 4 Pa, similar to that used for
charcoal samples by Braida et al. (2003). For the pore vol-
(mlliq g 1)
0.02219
ume evaluation, we employed aS-plot analysis, where the
0.2757
Vtotald
adsorption properties of a porous solid are compared with
–
–
–
those of a non-porous standard material exhibiting surface
chemistry similar to the test sample (Badalyan and Pendl-
(mlliq g 1)
eton, 2003). Moisture content was determined by compar-
0.00375
Vmicroc
0.2469
ison of sample mass before and after evacuation at 300 C.
We classified pore width (dp), according to IUPAC recom-
–
–
–
mendations as follows: micropores: dp < 2 nm, mesopores:
2 < dp < 50 nm, and macropores: dp > 50 nm. Pores, which
Sum DMb
were smaller than 2 nm were analyzed using the Horvath–
Kawazoe (H–K) method (Horvath and Kawazoe, 1983).
(%)
0.4
0.4
0.3
1.9
1.8
1.6
This method calculates the effective micropore size distri-
bution of slit-shape pores using the data from adsorption
isotherms. Using the H–K equation we calculated effective
Sum CMa
mean width of slit pores (dp), and correlated it with the
value of DV ads
Drslit
, where DVads is the incremental amount of
(%)
0.6
0.9
1.3
2.7
4.4
5.8
nitrogen adsorbed (converted to condensed liquid volume
of nitrogen) and Drslit is the corresponding incremental
width of slit pores. The individual and cumulative frequen-
(mg kg 1)
280
390
510
2 360
3 680
4 720
Mg
pyl-benzene, methanol, and dichloromethane with HPLC- a constant pressure of 22 psi. The detector was heated to
grade purity (>99.9%) were used in the experiments. For 250 C. The initial temperature of the oven was set to
practical reasons the sorbate concentrations were prepared 35 C, held for 3 min, and then ramped to 80 C with a rate
as ll l 1and converted into lg l 1 in the calculations. In the of 5 C min 1.
single-sorbate system, for the materials treated at 250 C
and 450 C, the initial sorbate concentrations were cover-
ing 2.20–87.90 lg ml 1 for benzene, and 2.17–86.6 lg ml 1 3. Results
for toluene. Due to the considerably higher sorption capac-
ity of the 850 C materials the concentration range was 3.1. Charcoal properties
expanded to 351.6 lg ml 1 for benzene and 346.4 lg ml 1
for toluene. In the bi-sorbate systems both sorbates were Charcoals combusted at 250 C and 450 C exhibited
added in equal amounts, the total sorbate concentration relatively low surface areas as revealed by N2-BET surface
therefore being doubled, compared to the single-sorbate area measurement, whereas the surface areas of the high
systems. In order to prevent varying solvent effects, metha- temperature treated charcoals (850 C) were very high
nol was always kept at 1% by volume throughout all (Table 1). The Red Gum charcoals exhibited a much bigger
experiments. Specifications regarding the maximum con- surface area than the Phalaris charcoals at corresponding
centration of carrier-solvent avoiding interference with temperatures. The ratio of the surface areas of the Red
the sorption process are inconsistent (e.g. Kleineidam Gum charcoals to the ones from Phalaris drops from 2 at
et al., 2002; Karapanagioti et al., 2004; Sander and Pigna- 250 C to 1.7 and 1.6 at the higher combustion tempera-
tello, 2005). However, we found in preliminary experiments tures. For both materials the outstanding increase of the
that keeping the solvent concentration constant at 1% pro- surface areas (by almost 20 times) occurred between
vided reproducible results. To avoid headspace (in order to 450 C and 850 C. This critical change was also docu-
minimize volatilization losses), the vials were filled up to mented by the pore size distribution of R450 and R850.
their capacity with Milli-Q water. As charcoal in such small The total pore volume of the 850 C material was higher
concentrations suspended in water would hardly settle by more than an order of magnitude than that for the
down during centrifugation, 0.32 ml of 1 M CaCl2-solution 450 C material (Table 1). Furthermore, the fraction of the
was added in order to support the flocculation. A final con- micropores (pores <2 nm), vmicro [mlliq g 1], revealed a
centration of 0.01 M CaCl2 was also chosen by other microporosity of 90% for the 850 C material, whereas
authors (Ahmad et al., 2001; Sander and Pignatello, the 450 C material did not exceed a microporosity of
2005). The vials were placed in the end-over-end shaker about 17%. The diagram displaying the integral pore size
again to equilibrate for 24 h. According to Braida et al. distribution indicated a relatively wide range of pore
(2003), at low initial concentrations (8 lg ml 1), benzene widths, i.e. 0.5–300 nm, the steep slope at about about
sorption reached an equilibrium after eight days, but 1.2 nm pore diameter indicating the large contribution of
the vast majority of benzene (>95%) was already sorbed this pore size for the 450 C material (Fig. 1). On the con-
within 24 h. For higher initial benzene concentrations trary, the range of pore size distribution for the 850 C
(1600 lg ml 1) the apparent equilibrium was shown to material was very narrow (Yu et al., 2006). Here, the over-
be reached after 24 h. Kwon and Pignatello (2005) reported all dominating pore sizes ranged from only 0.4–1 nm, with
that maximum sorption of benzene on the charcoal also insignificant participation of pores with a diameter >10 nm
utilized by Braida et al. (2003) was achieved within 20 h. (Fig. 1). Corresponding to the observed N2-BET surface
From these findings, together with observations that diesel areas, the pore size distribution illustrates the extraordi-
soot uptake of PAHs occurs within hours to one or two nary increase of the inner surface area with decreasing
days (Bucheli and Gustafsson, 2000) we concluded that diameter of the pores.
equilibration times of 24 h would be appropriate for our The total cation content of the Phalaris charcoals
purposes. The samples were then centrifuged at 650 g for exceeds the one of the Red Gum charcoals by a factor
a duration of 10 min. Subsequently, 5 ml of the superna- greater than four (Table 1). Differences in the cation con-
tant were transferred to PTFE-lined extraction vials with tents of grass and wood are also documented in literature.
15 ml capacity and extracted with 2 ml dichloromethane. Harmand et al. (2004) found a value of about 0.4% for the
Prior to extraction, propyl-benzene was added as an inter- sum of calcium, magnesium and potassium in Red Gum
nal standard. The extraction tubes were then shaken by wood (Eucalyptus camadulensis) from Cameroon. Consid-
hand vigorously and an aliquot of the solvent was trans- ering the low proportion of sodium contributing to the
ferred into PTFE-lined GC-vials. Analysis of the extracts total cation content of our Red Gum charcoal (2–5%),
was performed on a PERKIN ELMER Auto System Gas the findings of Harmand et al. (2004) are in line with our
Chromatograph equipped with a flame ionization detector data (Table 1). For a Phalaris species harvested between
(FID). The column was a DB-5 column with a length of July and October in Sweden, the sum of the four cations
30 m, an internal diameter of 0.25 mm and a film thickness also determined in our study was reported to be about
of 0.25 lm. The injection temperature was 200 C with 1 ll 1.8% of the dry matter (Burval, 1997), and thus again in
of sample injected. Helium was used as the carrier gas with good agreement with our data set (Table 1).
L.C. Bornemann et al. / Chemosphere 67 (2007) 1033–1042 1037
0.30 0.03
0.20 0.02
-1
0.10 0.01
R850
R450
0.00 0.00
0.1 1.0 10.0 100.0 1000.0
d p [nm]
Fig. 1. Integral pore size distribution of the charred material. Total pore volumes (vtotal) of R850 (ordinate on the left) and R450 (ordinate on the right),
plotted against the diameter of the pores (dp).
3.2. Influence of the combustion temperature on the and found Langmuir-type sorption isotherms for R850,
sorption process after the classification by Giles et al. (1960). Both, benzene
and toluene were sorbed by R850 to a much higher degree
Fundamental differences in the sorptive behaviour of than by the other materials. Comparing the respective coef-
benzene and toluene were found for the Red Gum materi- ficients of determination (R2) and especially the standard
als treated at different temperatures. In Fig. 2, we plotted errors of estimate (SEE), the isotherms from single and
the sorbed concentration of sorbate q [mg g 1] against bi-sorbate experiments on R850 showed considerably bet-
the final concentration in aqueous solution Cf [mg ml 1] ter fits to the Langmuir than to the Freundlich equation
(Table 2). The calculated maximum uptake (Smax) of each
sorbate in the bi-sorbate system was about half of the max-
1000 imum uptake in the single-sorbate systems, where benzene
a: Benzene and toluene were sorbed in comparable amounts (Table 2).
Sorption isotherms of R250 and R450 could successfully
100 be described with the model after Freundlich. For benzene,
R250 and R450 exhibited a comparable sorption, whereas
10 toluene expressed a slightly higher affinity to R450 com-
R250
R450 pared to R250 (Fig. 2 a and b). In contrast to R850, the
sorption of toluene on R450 and R250 was significantly
q [mg g ]
R850
-1
10 R250
3.3. Influence of the precursor material on the sorption
R450
R850 process
1
0.00 0.02 0.04 0.06 0.08 0.10 0.12 0.14 The apparent difference between the Phalaris- and Red
-1
C f [mg ml ] Gum-derived materials was the lower sorption capacity
of P850 as compared to R850 (Table 2). For P850, the cal-
Fig. 2. Sorbed amount of sorbate q plotted against the final sorbate
concentration Cf. Single-sorbate sorption isotherms for (a) benzene and culated maximum uptake after the Langmuir equation
(b) toluene on R250, R450, and R850. Error bars represent standard resulted in a value of Smax = 153 mg g 1, whereas the cor-
deviation of duplicate samples (n = 2). Symbols may cover error bars. responding value for the Red Gum charcoal was as large as
1038
Table 2
Results of model fits to single and bi-sorbate isotherms
Char type Temperature (C) Single-/bi-solute Sorbate Smaxa (mg g 1) KLb (ml mg 1) R2c (–) SEE d
(–) ne (–) KFf (mln mg1 n
g 1) R2g (–) SEE h
(–)
Langmuir model, whereas the isotherms for the maple of charcoal particles. Jonker and Koelmans (2002) found
wood char showed better fit to a Freundlich sorption iso- in their experiments that different solvents exhibited varying
therm. The sorption on charcoals produced at lower tem- abilities to extract PAHs from soot and sediments and pro-
perature in our study also fitted better to Freundlich model. posed a two-step mechanism. According to them, the PAHs
Kleineidam et al. (2002) investigated the sorption of dif- are being extracted by an initial swelling of the sorbent
ferent low-polarity organic compounds on a series of carbo- matrix with a subsequent displacement of sorbates by sol-
naceous adsorbents, covering humic soil organic matter, vent molecules. Among a selection of seven popular sol-
thermally altered carbon materials, and purely engineered vents, also comprising two mixtures of benzene and other
microporous sorbents. Employing the PM-model combined solvents, toluene was proven to be the best suited solvent
with linear partitioning for sorbents containing humic for the extraction of PAHs from charcoal. Therefore, the
material, they were able to predict unique sorption iso- enhanced sorption of benzene in the bi-sorbate systems
therms by employment of solubility normalized aqueous may result from a toluene-induced swelling of the matrix,
concentrations. Their results suggest that the PM-model is thereby opening up additional sorption sites for the smaller
the most appropriate model for sorption processes on benzene molecules and toluene itself being sterically hin-
highly porous materials. However, some concerns about dered to penetrate by its larger molecular size. Braida
potential artefacts resulting from enhanced water adsorp- et al. (2003) proved that certain benzene concentrations
tion to functional groups of sorbents with varying hydro- were able to induce the swelling of charcoal matrices,
philicity have been expressed (Li et al., 2005). Also recent thereby increasing the sorption capacity and inducing sorp-
results by Yang et al. (2006) showed that gaps in the under- tion hysteresis by pore deformation and solvent entrapment.
standing of the PM-model still exist. Their study revealed,
that the molar volume alone (as employed e.g. by Sander 4.2. Influence of the precursor material on the sorption
and Pignatello, 2005) in some cases may fail to be an appro- process
priate scaling factor in order to obtain matching isotherms
of hydrophobic compounds with varying molecular sizes. The lower (33%) sorption capacity of P850 compared
Although the PM-model is increasingly used for modelling to R850 (Table 2) is ascribed to the physicochemical differ-
of sorption processes, our results among with those of other ences between the respective materials. Although the expo-
researchers (e.g. Xia and Ball, 2000) show that the classical sure time to the heat treatment was already reduced due to
approaches like the Freundlich model and the Langmuir the more combustible nature of the grass, the charred grass
model may still be adequate in some cases. These models appeared to be much more disaggregated compared to the
are appropriate here, as the aim of our investigations was wood charcoal. A more extensive combustion, resulting in
to detect general differences in the sorptive properties of the loss of sorption active constituents may have resulted in
various charcoals, rather than seeking a specific mechanism the reduced sorption capacity. James et al. (2005) found
or an improvement in modelling of sorption isotherms. that surface area, pore volume, and microporosity are
The higher sorption of toluene in comparison with ben- not increasing endlessly with increasing combustion tem-
zene on R250 and R450 (Fig. 3a and b; Table 2) is possibly peratures, and that softening temperatures are also depen-
due to its higher hydrophobicity. However, toluene sorption dent on the precursor material. In their study, a heating
in single and bi-sorbate system was the same, showing no temperature of 820 C resulted in drastically reduced sur-
competitive effect. Sander and Pignatello (2005) examined face areas and microporosity for a charcoal from Betula
the competitive sorption of benzene, toluene, and nitroben- pendula, compared to charcoal produced at a temperature
zene on the charcoal mentioned above, which was also uti- of 700 C. For Auraucaria araucana, the softening temper-
lized by Zhu and Pignatello (2005). In their bi-sorbate ature was already reached at 450 C. Another explanation
experiments, the amount of competitive sorbate was kept for the reduced sorption capacities could be the overall
constant while the concentration of the test sorbate chan- higher cation content in Phalaris grass compared to Red
ged. From their resulting competitive sorption isotherms it Gum wood (Table 1). As the charcoal was weighed in as
can be seen that competition effects were most pronounced bulk, and was not corrected for its content of mineral con-
when the competitor solutes were added at high concentra- stituents, a higher cation content reduces not only the pro-
tions together with a low concentration of test sorbate. portion of highly sorptive BC in the bulk, but also increases
Competition effects diminished as the concentrations of the hydrophilic character of the whole sample. The latter is
the two competing sorbates converged. This explains the true as these cations are present as salts, their hydrophilic
lack of significant competition effect from either sorbate in character hindering the sorption of hydrophobic compo-
our bi-sorbate systems, as in our experiments both sorbates nents. Haghseresht et al. (1999) found that the content of
were always added in equal concentrations. aromatic carbon in the precursor correlated with the con-
In our bi-sorbate experiments, the sorption of benzene on tribution of amorphous carbon in the corresponding char-
R250 and R450 was even enhanced compared to the single- coal. A high amount of amorphous carbon results in an
sorbate system (Fig. 3a and b; Table 2). The reasons for this increased abundance of sorption-active edge sites as well
are unclear, but may be related to the ability of aromatic as in an increased disorder, thereby supporting the forma-
compounds like benzene and toluene to cause the swelling tion of micropores and increasing the sorption capacity
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(char): pseudo pore blockage by model lipid components and its behaviour of diuron in soil amended with charcoal. J. Agric. Food
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J. Agric. Food Chem. 2006, 54, 8545−8550 8545
Charcoal derived from the partial combustion of vegetation is ubiquitous in soils and sediments and
can potentially sequester organic contaminants. To examine the role of charcoal in the sorption and
desorption behaviors of diuron pesticide in soil, synthetic charcoals were produced through
Published on October 11, 2006 on http://pubs.acs.org | doi: 10.1021/jf061354y
carbonization of red gum (Eucalyptus spp.) wood chips at 450 and 850 °C (referred to as charcoals
BC450 and BC850, respectively, in this paper). Pore size distribution analyses revealed that BC850
contained mainly micropores (pores ≈ 0.49 nm mean width), whereas BC450 was essentially not a
Downloaded by UNIV OF GEORGIA on August 4, 2009
microporous material. Short-term equilibration (<24 h) tests were conducted to measure sorption
and desorption of diuron in a soil amended with various amounts of charcoals of both types. The
sorption coefficients, isotherm nonlinearity, and apparent sorption-desorption hysteresis markedly
increased with increasing content of charcoal in the soil, more prominently in the case of BC850,
presumably due to the presence of micropores and its relatively higher specific surface area. The
degree of apparent sorption-desorption hystersis (hysteresis index) showed a good correlation with
the micropore volume of the charcoal-amended soils. This study indicates that the presence of small
amounts of charcoal produced at high temperatures (e.g., interior of wood logs during a fire) in soil
can have a marked effect on the release behavior of organic compounds. Mechanisms of this apparent
hysteretic behavior need to be further investigated.
INTRODUCTION 30% of total organic matter in marine sediments (7) and 12-
31% of deep-sea sediments (8), 18-41% of the soils and
Black carbon (e.g., soot and charcoal) produced from the
sediments collected from the suburban area of Guangzhou,
incomplete combustion of vegetation and fossil fuel is ubiquitous
China (9), up to 30% of soils collected around Australia (4,
in terrestrial and aquatic environments (1, 2). In addition to
10), and up to 45% of total organic carbon (TOC) in soils
dispersal through biomass and fossil fuel combustion in the
collected from Germany (11).
environment, some agricultural practices may also contribute
to the increasing amount of black carbon in agricultural soils. It has been well recognized that the presence of charcoal in
For example, it is an old practice in the eastern and southern soil could not only enhance the sorption of organic contaminants
parts of China to mix firewood ashes with soils and livestock such as pesticides (12) but also influence the nature of the
dung followed by heating and aging for several months, before sorption mechanism (13). Research in recent years (14) has
the mixture is added directly into the field as a fertilizer. Direct shown that the residues produced from burning wheat and rice
burning of plant residues in the field after harvest for land were 400-2500 times more effective than soil in sorbing diuron
clearing is common all over the world. Such agricultural over the concentration range of 0-6 mg/L in water. However,
practices will also provide direct input of black carbon into the effect of these amendments on the desorption behavior of
agricultural soil (3-6). Terrestrial black carbon, being erosion- diuron was not investigated in that study.
prone, is readily transported by wind and water and is often The nature and properties of black carbon are strongly
deposited into aquatic ecosystems. Black carbon has been found affected by the nature of parent materials (wood, grass) and
to make a significant proportion of soils and sediments: 15- the temperature experienced during combustion (2, 15). Char-
coals formed from lignocellulosic materials under conditions
* Corresponding author (e-mail rai.kookana@csiro.au; fax +61 8 of pyrolysis become increasingly carbonized as temperatures
83038565).
† CSIRO Land and Water.
rise above 500 °C and are completely carbonized as temperatures
‡ Jiangsu Academy of Agricultural Sciences. approach 1000 °C (15). Under relatively high pyrolysis tem-
§ Chinese Academy of Sciences. peratures (500-700 °C), the charcoal derived from wheat was
10.1021/jf061354y CCC: $33.50 © 2006 American Chemical Society
Published on Web 10/11/2006
8546 J. Agric. Food Chem., Vol. 54, No. 22, 2006 Yu et al.
found to be well carbonized and had a relatively high surface value of ∆Vads/∆rslit, where ∆Vads is the incremental amount of nitrogen
area and low oxygen content (16). Such chars have been reported adsorbed (converted to condensed liquid volume of nitrogen) and ∆rslit
to show high affinity for organic compounds (16, 17), especially is the corresponding incremental width of slit pores. The individual
for polar solutes (16). and cumulative frequencies were calculated for a range of dp data. Other
properties of these chars as characterized using NMR techniques have
Despite the fact that the environmental fate and impact of
been published elsewhere (27).
contaminants (bioaccessibility, bioavailability, and toxicological The soil used in this experiment was collected from the Roseworthy
impact) are strongly influenced by their desorption behavior Campus, University of Adelaide, and was amended with charcoal. After
(18-21), the effect of black carbon on the desorption behavior air-drying, the soil was passed through a 2 mm sieve. This soil contained
of compounds has so far received limited attention. Braida et 87.8% sand, 1.3% silt, 8.3% clay, and 1.4% organic matter and is of
al. (22) observed pronounced hysteresis in the sorption of sandy loam texture. The soil pH value was 6.8 in a 1:5 (soil/water)
benzene in water to pure-form maple-wood charcoal prepared soil suspension and had a maximum water-holding capacity of 34.2%
by oxygen-limited pyrolysis. Here they found that the sorption (v/v) and a cation exchange capacity of 9.3 cmol(+)/kg. The soil was
of wood charcoal was highly irreversible and proposed that sterilized by autoclaving at 120 °C under 300 kPa chamber pressure
hysteresis was due to pore deformation of charcoal during for 30 min three times within 3 days.
desorption of the sorbate, leading to entrapment of molecules Charcoal-amended soils used in the experiment were prepared by
mixing the above soil and the two types of charcoal at different ratios.
as the polyaromatic scaffolding collapsed during desorption.
The percentages of charcoal materials in the amended soils were 0,
The objective of this study was to assess the effect of the 0.1, 0.5, 1.0, 2.0, and 5.0% (w/w) for BC450 and 0, 0.1, 0.2, 0.5, 0.8,
presence of small amounts of charcoal materials (prepared from and 1.0% (w/w) for BC850. The charcoal-amended soils were thor-
eucalyptus wood at two different temperatures of 450 and oughly mixed on a rotary shaker for 7 days before their use as sorbents
850 °C) in soil on the sorption-desorption behaviors of pesti- for sorption and desorption experiments.
cides in soil. Sorption and desorption behaviors were investi- Sorption and Desorption Isotherms. Diuron sorption by the
Published on October 11, 2006 on http://pubs.acs.org | doi: 10.1021/jf061354y
gated to assess the role of the types and amounts of charcoal as sorbents was measured by the batch equilibration technique. Preliminary
sorbent for pesticides (represented by diuron as a model nonionic kinetic experiments showed sorption and desorption of diuron in
pesticide) in soils amended with various amounts of charcoals. charcoal-amended soils reached an apparent equilibrium within 24 h.
Downloaded by UNIV OF GEORGIA on August 4, 2009
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Science of the Total Environment 354 (2006) 170 – 178
www.elsevier.com/locate/scitotenv
Abstract
This study evaluated the bioavailability of diuron in soil as influenced by char arising from the burning of wheat straw. The wheat
char was a highly effective sorbent for diuron. The presence of 1% wheat char in soil resulted in a 7–80 times higher diuron sorption.
A 10-week incubation resulted in b40% of 0.5 mg/kg diuron in 0.5% char-amended soil microbially degraded, as compared to 50%
in char-free soil under the same conditions. Over the experimental range of diuron application rates from 0 to 12 mg/kg and of char
contents from 0% to 1.0%, a 4-week bioassay indicated that both the barnyardgrass survival rating and the fresh weight of
aboveground biomass decreased with increasing diuron application at given char contents but increased with increasing char content
at potentially damaging diuron application rates. Residual analyses of bioassayed soils showed that the soils with char contents of
0.5% and higher and diuron application rates of 3.0 mg/kg and higher, as compared to those with no or low (0.05%) char and a diuron
application rate of 1.5 mg/kg, had higher residual diuron levels but higher barnyardgrass survival ratings and fresh weights. These
results suggest that enhanced sorption of diuron in soil in the presence of wheat char reduced the bioavailability of diuron, as
manifested by reduced microbial degradation of diuron and its herbicidal efficacy to barnyardgrass. This study may have greater
implication than for burning of wheat straw that field burning of vegetations may reduce bioavailability of pesticides.
D 2005 Elsevier B.V. All rights reserved.
lished that phytotoxicity of herbicides is directly derived chars may be the reduced bioavailability of
related to their concentrations in the soil solution pesticides in soils to both microbes and plants. The
(e.g., Lambert, 1966; Pillay and Tchan, 1971). It is reduction in microbial degradation of benzonitrile in a
generally true that only dissolved nutrients and soil in the presence of wheat char has been reported
organic chemicals in the soil interstitial bulk-like (Zhang et al., 2004). Reduced microbial degradation
water (i.e., plant-available water above the wilting increases the persistence of pesticides and thus the
point) are available for plant-root uptake. Sorption environmental risk associated with pesticide use. The
largely controls concentrations of organic contami- high sorptivity of crop-residue-derived chars may also
nants in the soil solution and thus is the major reduce herbicidal efficacy to weeds. Poor herbicidal
determinant of the bioavailability of pesticides to both efficacy is a concern both economically and environ-
microorganisms and plants. Enhancing sorption by mentally due to additional application of herbicides
increasing soil organic matter content leading to a for weed control.
reduction in the solution-phase concentrations results In this study, we determined the bioavailability of
in a decreased microbial degradation of organic diuron to soil microorganisms and to barnyardgrass
contaminants (e.g., Guerin and Boyd, 1993). Charcoal (Echinochloa crus-galli (L.) Beauv.) in soil in the
dipping or banding effectively protects many plants presence of wheat-straw-derived char. Use of bar-
from herbicidal injury (Arle et al., 1948; Burr et al., nyardgrass, a common rice weed, has both agronomic
1972; Chandler et al., 1978; Jordan and Smith, 1971; and environmental significance. Our objectives were
William and Romanowski, 1972). to determine the microbial degradation of diuron and
Sorptive properties of agricultural soils, and thus its efficacy to barnyardgrass in relation to soil
bioavailability of pesticides, are often influenced by sorption in the presence of wheat char and to evaluate
agricultural practices. Field burning of crop residues the impact of crop-residue-derived chars on the
worldwide incorporates the resulting chars into soils. bioavailability of pesticides in soil. Results from
Hilton and Yuen (1963) postulated that the retained laboratory measurements and greenhouse bioassays
sorptivity of many Hawaiian soils for ureas and s- indicated that wheat char was a highly effective
triazines after oxidative removal of soil organic matter sorbent for diuron and its presence in soil resulted in
by hydrogen peroxide was a result of the peroxide- enhanced diuron sorption and subsequently dimin-
resistant soil chars arising from burning of sugarcane ished bioavailability.
trash. Toth et al. (1999) observed a reduction in the
phytotoxicity of diuron applied over the ash of
recently burned kangaroo grass, due primarily to the 2. Materials and methods
diuron sorption by the ash. We confirmed their
postulation by measuring the sorption of pesticides 2.1. Materials
on soil-free chars from burning of crop residues.
Sorption of diuron by the chars from burning of wheat Wheat char used in this study was from our
straw and rice residue was 400–2500 times higher previous studies (Yang and Sheng, 2003a,b). Air-
than that by a soil with 2.1% organic matter (Yang and dried wheat (Triticum aestivum L.) straw (10 kg) was
Sheng, 2003a). Amendment of the soil with the wheat collected from the Arkansas Agricultural Research
char up to 1% (by weight) enhanced the sorptivity of and Extension Center in Fayetteville, Arkansas.
the soil for diuron in proportion to the char content. Wheat char was obtained by burning the straw on a
The char aged in the soil for one month remained stainless steel plate (1 m 1 m) in an open field under
highly effective for diuron sorption and dominated the natural conditions in a July afternoon. The BET
sorption, although a small reduction (b30%) in surface area of the char was determined to be 10.1 m2/
sorptivity was observed (Yang and Sheng, 2003b). g in a commercial service laboratory. Chemical
Further aging of the char for up to 12 months did not analysis showed that the char contained 13% elemen-
result in a further sorptivity reduction, indicating that tal carbon and 42% silica.
the char was resistant to degradation. One direct Soil, classified as Stuttgart silt loam, was collected
consequence of the high sorptivity of crop-residue- at the Rice Research and Extension Center, Stuttgart,
172 Y. Yang et al. / Science of the Total Environment 354 (2006) 170–178
Arkansas. The soil had a mechanical composition of equilibration technique. Various quantities of diuron
17.1% sand, 60.4% silt, and 22.5% clay. The soil in 0.005 M CaCl2 solution were added into 25-ml
contained 2.1% organic matter and had a cation- Corex glass centrifuge tubes containing sorbents with
exchange capacity of 8.5 cmolc/kg. The soil, without a constant mass between 0.01 and 3.5 g. The mass of
records of crop residue burns, was presumed to contain sorbents was adjusted to allow for N40% of added
minimal levels of chars. The soil was air-dried, ground, diuron to be adsorbed. Additional 0.005 M CaCl2
and passed through a 1-mm sieve. Char-amended soils solution was added to bring the total liquid volume to
were prepared by thoroughly mixing soil with accu- 10 ml. Initial concentrations of diuron ranged from
rately weighed char in exact char contents of 0.05%, 1.25 to 12.5 mg/l. The tubes were closed with Teflon-
0.1%, 0.5%, and 1.0% (by weight). lined screw caps and rotated (40 rpm) at room
Diuron with a purity of 99% was purchased from temperature (~25 8C) for 48 h. Other measurements
ChemService (West Chester, PA) and used as received. have shown that sorption of diuron by both the soil
Diuron is an electroneutral molecule. The pesticide has and the char reached apparent equilibria within 24 h;
a water solubility of ~42 mg/l and a log K ow of 2.68 at the sorption by char-amended soil was thus assumed
room temperature (Howard and Meylan, 1997). The to also reach equilibrium within the same duration.
Henry’s Law constant of 2.710 6 atm m3/mol After the establishment of sorption equilibria,
indicates that the pesticide is non-volatile and therefore sorbents and aqueous phases were separated by
suitable for prolonged laboratory and greenhouse centrifugation at 6000 rpm (RCF=5210 g) for 30
studies. Diuron is a urea compound primarily used as min. The diuron concentrations in supernatants were
a preemergence herbicide in soils to control germinat- analyzed by high-performance liquid chromatography
ing grasses and broad-leaved weeds. As a photosyn- (HPLC). The amount of diuron sorbed was calculated
thesis inhibitor, diuron injures weeds with symptoms from the difference between the amount initially
of foliar chlorosis concentrated around veins (some- added and that remaining in equilibrium solution.
times interveinal) followed by necrosis. All measurements were in duplicate with a variation
A mixed diuron-degrading culture was isolated generally b5%, and the calculated average data were
from soil collected in a cotton field where diuron has reported. The measurements with blanks not contain-
been applied annually for over 15 years. One gram of ing sorbents found that glass tubes did not adsorb
the soil was inoculated into 100 ml of medium diuron and no processes other than sorption con-
containing mineral salts (Stanier et al., 1966), 0.1 ml tributed to the loss of solution-phase diuron.
of vitamin solution (Wolin et al., 1963), and saturated
diuron. The mixture was incubated for 1 week at 28 2.3. Microbial degradation of diuron
8C on a platform shaker at 150 rpm. After two serial
transfers to fresh medium, the culture enrichment was Sterilized soil and 0.5% char-amended soil (200 g
obtained. Preliminary tests showed that the isolated each) were placed in 1000-ml glass beakers, spiked
culture readily degraded diuron in solution. with 2 ml of 50 mg/l diuron stock solution in acetone,
Barnyardgrass seeds, collected from the plant thoroughly mixed, and allowed for acetone to
grown in a rice field in Stuttgart, AR in 1983, were evaporate for 2 days. The soils were then watered
acid-scarified in 1 N nitric acid for 1 h at room to near the field capacity and aged for another 2 days
temperature. The seeds were washed with deionized to allow the diuron sorption to complete. Three 5-g
water, spread evenly on filter paper in petri dishes, samples from each of the soils were extracted with 5
covered with another filter paper, watered with 3 ml of ml of H2O and 5 ml of water-saturated ethyl acetate
deionized water, and incubated in the dark at room for 72 h. Following the phase separation, 2 ml of
temperature for 72 h for germination. ethyl acetate were dried under N2 gas and redissolved
in 1 ml of methanol. The diuron concentrations in
2.2. Sorption isotherms for diuron methanol were analyzed by HPLC. The recoveries
were 95.2% and 85.2% for soil and char-amended
Sorption of diuron by soil, wheat char, and 1% soil, respectively. Each soil was inoculated with 5 ml
char-amended soil was measured by the batch of the isolated culture enrichment. Preliminary tests
Y. Yang et al. / Science of the Total Environment 354 (2006) 170–178 173
found that 5 ml of the enrichment in 200 g of soil The survival rating was performed independently by
gave an appreciable degree of diuron degradation in three individuals. Average survival ratings were
one week. The soils were thoroughly mixed again. calculated using the data from the replicated samples
The beakers were then covered with aluminum foil from all the individuals. Four weeks after planting,
and placed in the dark at room temperature. Three 5-g plants were cut at the soil level and immediately
soil samples from each beaker were taken weekly for weighed to obtain the fresh weights of the above-
10 weeks for diuron analysis. The soils were ground biomass. All the visual survival rating and
extracted following the same extraction procedures fresh weight data were statistically analyzed using the
as those for the recoveries, except that extracting SAS program.
water contained 0.5% Ag2SO4 to immediately termi- Following the bioassay, the soil samples of selected
nate biodegradation. The diuron concentrations were treatments were analyzed for residual diuron by
adjusted for the recoveries. The soils, watered when HPLC using the extraction procedures described
necessary, were maintained moist throughout the earlier. The average diuron concentration of the
degradation experiment. replicate soils of the same treatment was reported.
The soils from the following 6 treatments were
2.4. Barnyardgrass bioassay for diuron selected based on the char contents, diuron rates,
and barnyardgrass aboveground fresh weights: S0-0,
A series of 4 diuron solutions with concentrations S0-1.5, S0.05-1.5, S0.5-3.0, S1-3.0, and S1-6.0,
of 60, 120, 240, and 480 mg/l in acetone were where the suffix C-D to S represents the char content
prepared. Five milliliters of each of the solutions, (C)-applied soil concentration of diuron (D).
along with acetone only, were added to 200 g of char-
free soil or char-amended soils in plastic bags, 2.5. Analysis of diuron
resulting in the diuron levels of 0, 1.5, 3.0, 6.0, and
12 mg/kg in the soils, respectively. The five diuron Diuron in the supernatants from sorption experi-
levels were referred to as 0X, 1X, 2X, 4X, and 8X, ments and in the extracts from microbial degradation
where X=1.5 mg/kg and is within the range of and greenhouse bioassay tests was analyzed on a
recommended field application rates. The five char Hitachi reversed-phase high-performance liquid chro-
contents were 0%, 0.05%, 0.1%, 0.5%, and 1%. The matograph (Hitachi High-Technologies Tokyo,
combination of the 5 diuron rates and the 5 char Japan) fitted with a UV-visible detector set at the
contents resulted in a total of 25 treatments. Each maximum absorption wavelength for diuron (252
treatment was in triplicate. The soils were thoroughly nm). A Phenomenex Prodigy C18 column was used
mixed in the bags, and transferred to plastic cups (Alltech Assoc., Deerfield, IL). The mobile phase
following the evaporation of acetone from the opened was a mixture of acetonitrile and water (50:50, v/v)
bags. at a flow rate of 1.0 ml/min. The injection volume
A small quantity of soil (~20 g) was first removed was 20 Al.
from each cup. Ten pregerminated barnyardgrass
seeds with extended radicles and hypocotyls were
placed evenly on the soil surface in each cup and then 3. Results and discussion
covered with the previously removed soil. Following
planting, the cups were placed in a completely Isotherms for the sorption of diuron by soil, wheat
randomized block design in a greenhouse, watered char and 1% char-amended soil are presented in Fig.
with 40 ml of deionized water, and maintained moist 1, in which the amount of diuron sorbed (mg/kg) is
throughout the experiment. The greenhouse was plotted against the equilibrium concentration (mg/l) in
maintained at 34/20 8C day/night temperatures with water. No single mathematical models provided
a 14-h lighting cycle. Barnyardgrass seedling survival adequate fits for the sorption data. The curves were
was visually rated two weeks after planting as percent drawn to assist in visualization and comparison of the
of survival between 0 and 100, with 0% representing data. Soil effectively sorbed diuron, rather consistent
no survival and 100% complete survival (no injury). with the prediction from the log K ow value of diuron
174 Y. Yang et al. / Science of the Total Environment 354 (2006) 170–178
100
Amount of Diuron Sorbed (mg/kg)
enhanced sorption in the presence of wheat char rate at a given char content and decreased with
reduced the bioavailability of diuron to soil micro- increasing char content at a given diuron application
organisms. Reduced biodegradation of benzonitrile by rate. The observation is consistent with the earlier
a bacterium in soil in the presence of wheat char was sorption measurements that the presence of wheat
also due to enhanced sorption (Zhang et al., 2004). In char enhanced the diuron sorption by soil. By four
addition to elemental carbon and silica, wheat char weeks after planting (prior to cutting), uninjured
contained 21% potassium, 1.5% phosphorous, 0.64% barnyardgrass showed continued growth, whereas
nitrogen, and other microelements (Yang and Sheng, injured ones did not recover (Fig. 3).
2003b). When in their available forms in soil, some of More quantitative barnyardgrass bioassay to eval-
these nutrients may stimulate microbial activity. We uate the impact of wheat char on the bioavailability of
have found that when benzonitrile was not limiting, diuron was obtained by visually rating barnyardgrass
1% wheat char provided nutritional stimulation on survival two weeks after planting and by weighing
benzonitrile degradation (data not shown). Such a aboveground fresh biomass four weeks after planting
stimulation on diuron degradation in 0.5% char- (Fig. 4). Without application of diuron, barnyardgrass
amended soil was not obvious. was somehow injured in char-free soil. In the presence
Fig. 3 is the photograph comparing the barnyard- of wheat char (z0.05%), the injury was eliminated.
grass growth among the soil samples subjected to This suggests that unknown herbicides likely phyto-
diuron applications in the absence and presence of toxic to barnyardgrass may be present in char-free soil
wheat char just prior to cutting the plants for their but deactivated by the char. A full rate of diuron (1.5
fresh weights. The samples consisted of 25 cups, each mg/kg) in char-free soil showed almost complete
representing one of the three replicates for each of all injury to barnyardgrass. However, both the barnyard-
the treatments, and were placed de-randomized to aid grass survival rating and fresh weight increased with
visualization. In the absence of diuron application, increasing char content. A char content of 0.5% or
barnyardgrass showed a normal growth without higher was sufficiently high that diuron completely
observable growth stimulation by wheat char lost its efficacy to barnyardgrass. The application rates
nutrients. One week after planting, the barnyardgrass of 3 mg/kg and higher resulted in complete-to-partial
injury was obvious (photograph not shown). The losses of diuron efficacy to barnyardgrass. Similar to
injury increased with increasing diuron application the observations with the full rate of diuron, the
Wheat Char in Soil (%)
1.0
0.5
0.1
0.05
0.0
(a) (b)
100 0.05
(%)
0.04
)
80
Fresh Weight (g
Survival Rating
60 0.03
40 0.02
)
0.5 0.5
(%
(%
0 0.1 0.00 0.1
nt
nt
0 0.05 0 0.05
nte
n te
1.5 3.0 0 Co 1.5 3.0 0
Co
Rate 6.0 Rate 6.0
of Diu 12 of Diu 12
ron (m
ar
ar
ron (m
g/kg)
Ch
Ch
g/kg)
Fig. 4. Growth of barnyardgrass in soils as a function of diuron application rate and wheat char content showing (a) survival rating of
barnyardgrass two weeks after planting, and (b) fresh weight of barnyardgrass four weeks after planting.
survival rating and fresh weight at higher application contained residual diuron with levels of about 40–
rates increased with increasing char content over the 49% of their respective application rates. The soils S0-
tested range of char contents in soil. The Student’s t 1.5 and S0.05-1.5 containing no or low char (0% and
test at the 95% level of confidence (a=0.05) was used 0.05%, respectively) had residual diuron concentra-
to compare the individual survival ratings and fresh tions of ~0.7 mg/kg and produced much lower
biomass weights at various char contents and diuron barnyardgrass fresh weights than the soil S0-0,
application rates. Survival ratings and fresh weights indicating the availability of diuron to barnyardgrass
were statistically different (a=0.05) for V0.05% char in these soils. Although the soils S0.5-3.0 and S1-3.0
with no diuron application, for V0.5% char with 1.5 containing 0.5% and 1% char, respectively, had
mg diuron/kg, for z0.1% char with 3.0 mg or 6.0 mg residual diuron concentrations almost twice those in
diuron/kg (fresh weights were significantly different the soils S0-1.5 and S0.05-1.5, the barnyardgrass
forz0.5% char with 6.0 mg diuron/kg), and for fresh weights associated with the former two soils
z0.5% char with 12 mg diuron/kg. These results were much higher than those with the latter two. In
suggest the decreased bioavailability of diuron to fact, the barnyardgrass fresh weights with the soils
barnyardgrass with increasing char content in soil, due
presumably to enhanced sorption of diuron in the Table 1
presence of the char. Relationship between measured residual concentrations of diuron
The sorptive role of wheat char in reducing diuron and barnyardgrass fresh weights in selected soil and char-amended
bioavailability (efficacy) to barnyardgrass is con- soil samples subjected to various treatments four weeks after
firmed by measuring residual concentrations of diuron planting as influenced by percent char content and application rate
of diuron
in soils after cutting barnyardgrass. Soils from 6
selected treatments, where barnyardgrass fresh Soil Char Rate of Barnyardgrass Residual
content diuron fresh fresh weight (g) concentration
weights differed significantly, were analyzed for (%) weight (g) (mg/kg)
residual diuron. The concentrations in the three
S0-0 0 0 0.0242 0.00
replicate soils of each treatment were highly invariant, S0-1.5 0 1.5 0.0007 0.73
with the difference b4.3%. The average concentra- S0.05-1.5 0.05 1.5 0.0030 0.69
tions were calculated and presented in Table 1. Char- S0.5-3.0 0.5 3.0 0.0224 1.28
free soil (S0-0) did not contain a measurable level of S1-3.0 1 3.0 0.0308 1.20
S1-6.0 1 6.0 0.0378 2.42
diuron. All other soils that had received diuron
Y. Yang et al. / Science of the Total Environment 354 (2006) 170–178 177
Pillay AR, Tchan YT. Phytotoxicity of diuron in some Australian William RD, Romanowski RR. Vermiculite and activated carbon
soils. Proc Weed Soc NSW 1971;IV:21 – 4. adsorbents protect direct-seeded tomatoes from partially selec-
Shimp RJ, Young RL. Availability of organic chemicals for tive herbicides. J Am Soc Hortic Sci 1972;97:245 – 9.
biodegradation in settled bottom sediments. Ecotoxicol Environ Wolin EA, Wolin MJ, Wolfe RS. Formation of methane by bacterial
Saf 1988;15:31 – 45. extracts. J Biol Chem 1963;238:2882 – 6.
Stanier RY, Palleroni NJ, Doudoroff M. The aerobic pseudomonads: Yang Y, Sheng G. Enhanced pesticide sorption by soils containing
a taxonomic study. J Gen Microbiol 1966;43:159 – 271. particulate matter from crop residue burns. Environ Sci Technol
Steen WC, Paris OF, Baughman GL. Effects of sediment sorption 2003a;37:3635 – 9.
on microbial degradation of toxic substance. In: Baker RA, Yang Y, Sheng G. Pesticide adsorptivity of aged particulate matter
editor. Contam Sediments, vol. 1. Ann Arbor, MI7 Ann Arbor arising from crop residue burns. J Agric Food Chem
Science Publ.; 1980. p. 477 – 82. 2003b;51:5047 – 51.
Toth J, Milham PJ. Activated-carbon and ash-carbon effects on Zhang P, Sheng G, Wolf DC, Feng Y. Reduced biodegradation
the adsorption and phytotoxicity of diuron. Weed Res 1975; of benzonitrile in soil containing wheat-residue-derived ash.
15:171 – 6. J Environ Qual 2004;33:868 – 72.
Toth J, Milham PJ, Kaldor CJ. Decreased phytotoxicity of diuron
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J. Pestic. Sci., 33(3), 266–270 (2008)
DOI: 10.1584/jpestics.G08-08
Note
bile phase containing a gradient mixture of acetonitrile and water strain FJ1117YT and each member of CD7 were extracted from
(20%/80% 0 min–20%/80% 5 min, linear gradient–40%/60% 11 suspensions of bacterial colonies grown on R2A agar (Difco)
min, and linear gradient–20%/80% 15 min–20%/80% 20 min). plates by a protocol for gram-positive bacteria of DNeasy Blood
The injection volume was 50 m l and the eluted compounds were & Tissue Kit (QIAGEN). Nucleotide sequences of 16S rRNA
detected by UV at 220 nm. Metabolites of s-triazines were deter- genes of isolated bacteria were analyzed by direct sequencing of
mined using LC-ESI-MS. Separation was achieved using LC Al- the PCR products described previously.5)
liance 2695 (Waters) system equipped with the same ODS col-
umn as above (40°C). A mixture of acetonitrile/0.2% acetic acid 5. Denaturing gradient gel electrophoresis (DGGE) analy-
was used as the eluent (5%/95% 0 min, linear gradient–50%/50% sis
10 min–80%/20%10.1 min–80%/20% 15 min, and linear gradi- Touchdown PCR was performed with a TP600 thermal cycler
ent–5%/95% 20 min). The injection volume was 10 m l. The ESI- (Takara BIO) using GoTaq Green Master Mix (Promega). GM5F-
MS system was Quattro micro API (Waters) with the flow rate of gc-clamp and R534,13) primers designed from a sequence of the
nebulization set at 100 l/h and the flow rate for desolvation gas variable V3 region of 16S rRNA, were used for PCR. DGGE
(N2) set at 500 l/h. The respective temperatures of source and analysis was performed using 6% polyacrylamide gel (ratio of
desolvation were set at 100 and 350°C; and capillary voltage was acrylamide to bisacrylamide 37.5 : 1) in 1TAE (40 mM Tris
3.5 kV. Detection was performed by scanning between m/z 100 base, 20 mM acetic acid, and 1 mM EDTA) with a 30% to 60%
and m/z 300 under cone voltage of 35 V in positive ion mode. denaturant gradient (100% denaturant containing 7 M urea and
Cyanuric acid was detected at m/z 128 [MH] under cone volt- 40% formamide). Electrophoresis was performed at a constant
age of 23 V in negative ion mode, and simazine-2-hydroxy was voltage of 150 V and at a temperature of 60°C for 3.5 h by using
m/z 184 [MH] under cone voltage of 35 V in positive ion the DcodeTM universal mutation detection system (Bio-Rad).
mode. After electrophoresis was completed, the gel was stained with
SYBR gold (Invitrogen) for 20 min, rinsed, and the bands were
3. Enrichment of Charcoal A100 with strain FJ1117YT and visualized with a Molecular Imager Pharos FX plus system (Bio-
CD7 Rad).
Charcoal A100 (Toyo Denka Kogyo) was used as the enrichment
material. Enrichment of charcoal with a bacterial consortium was 6. Simultaneous degradation of chloro- and methylthio-s-tri-
performed using a charcoal perfusion method, which was modi- azines using Charcoal A100 enriched with strain
fied from the soil perfusion method described by Audus.12) First, FJ1117YT and CD7
washed Charcoal A100 (7.5 g, dry weight) was packed in perfu- Charcoal A100 enriched with strain FJ1117YT and CD7 (0.4 g
sion apparatus equipped with glass sintered filter, and then auto- dry weight) was inoculated in MM (30 ml) containing 5 mg/l
claved. Subsequently, three pieces of stab cultures of CD7 on a each of simazine, atrazine, simetryn, and dimethametryn or in
MM agar plate containing 40 mg/l simazine were placed on the MMS containing 5 mg/l of each herbicide in 50 ml flasks. The
charcoal, and the charcoal layer was covered with glass fiber filter flasks were shaken at 120 rpm at 25°C for 15 days. As controls,
paper. Enrichment was performed in the dark at 25°C. MM (300 sterile Charcoal A100 and/or Charcoal A100 enriched with only
ml) containing 5 mg/l simazine was perfused with air lift using an CD7 were inoculated and shaken under the same conditions. The
air pump for 14 days. The concentration of simazine in the perfu- concentration of s-triazines in the medium was determined peri-
sion fluid was determined by HPLC, and the perfusion fluid was odically by HPLC. Cyanuric acid, simazine-2-hydroxy, and hy-
replaced twice. After 14 days, the glass fiber filter paper was re- droxy analogues of atrazine and dimethametryn in the medium
placed. A phosphate buffer suspension of strain FJ1117YT was after 15 days were measured by LC-ESI-MS.
placed on the filter paper. MM (300 ml) containing 5 mg/l
simazine, 5 mg/l simetryn was perfused under similar conditions
Results and Discussion
for 21 days, and the perfusion fluid was replaced once during the 1. Enrichment of Charcoal A100 with a bacterial consor-
perfusion process. Lastly, MM (300 ml) containing 5 mg/l sime- tium
tryn was used as perfusion fluid for 38 days, and was replaced The extent of enrichment of Charcoal A100 with strain
once. The vitamin mixture was added twice. Total enrichment FJ1117YT and CD7 was determined from the change in the con-
time was 73 days, and this material was used thereafter. Non-en- centration of simazine and simetryn in the perfusion fluid. In the
riched Charcoal A100 was also perfused as a control under the first step of enrichment, CD7 was enriched in Charcoal A100.
same conditions. Concentration of simazine in the CD7-inoculated charcoal de-
creased faster than the control, and the degradation rate of
4. Preparation of DNA and analysis of 16S rRNA gene simazine increased with every replacement of the perfusion fluid
Adherent bacteria on the surface of Charcoal A100 enriched with (data not shown). The charcoal was subsequently further enriched
strain FJ1117YT and CD7 were removed by sonication in phos- with strain FJ1117YT and perfused with MM containing
phate buffer for 2 min. Charcoal A100 inhabited with strain simazine and simetryn. Simazine was degraded almost immedi-
FJ1117YT and CD7 was pulverized, and total DNA was ex- ately (Fig. 1-A until Day21), in contrast to the slow degradation
tracted with Fast DNA Kit for soil (Q-Bio gene). Total DNA of of simetryn (Fig. 1-B until Day21). The disappearance rate of
268 K.-i. Yamazaki et al. Journal of Pesticide Science
Fig. 1. Enrichment of strain FJ1117YT and CD7 in Charcoal A100 using a charcoal perfusion method. Changes in the concentrations of
simazine (A) and simetryn (B) during enrichment are illustrated (both figures overlapped until 21 days). Charcoal A100 without enrichment was
used as a control. In order to enrich CD7, MM containing 5 mg/l simazine was perfused for 14 days before these data. The arrows indicate as fol-
lows: replacement with MM containing simazine and simetryn (black), replacement with MM containing simetryn (white), and addition of vita-
min mixture (striped).
simetryn was initialing almost the same as that of control, but in- less than 0.1 mg/l and hydroxy analogues of atrazine and
creased after the second perfusion (Fig. 1-B on Day8). The de- dimethametryn were not detected (data not shown). This result
crease of pesticides in sterile Charcoal A100 was considered to suggests that hydroxyl analogues of methylthio-s-triazines, which
occur because pesticides were adsorbed on Charcoal A100. In can not be metabolized by strain FJ1117YT, were mineralized by
order to aid the growth of strain FJ1117YT,9) vitamin mixture CD7 via N-ammelide analogue and cyanuric acid. These results
was added but had little effect on the enrichment of FJ1117YT. also indicate that methylthio-s-triazines could be mineralized by
However, because the enrichment of CD7 was sufficient, MM the bacterial consortium that included strain FJ1117YT and CD7.
containing simetryn without simazine was further perfused (Fig. In conclusion, the respective degradation abilities of CD7 and
1-B after Day21), and the degradation rate of simetryn was fur- strain FJ1117YT were successfully maintained in Charcoal
ther increased. This result indicates the enrichment of strain
FJ1117YT in Charcoal A100.
Fig. 3. Time course of simultaneous degradation of chloro- and methylthio-s-triazines with Charcoal A100 enriched with strain FJ1117YT
and CD7. Degradation of simazine (A), atrazine (B), simetryn (C), and dimethametryn (D) by strain FJ1117YT and CD7 with () or without
() sulfate, with CD7 alone (), and using non-enriched Charcoal A100 as a control () are shown.
A100. Chloro- and methylthio-s-triazines were degraded simulta- coal A100 enriched with strain FJ1117YT and CD7 could be a
neously and their metabolites were hardly detected. The expected promising model to construct a multifunctional material enriched
metabolic pathways of chloro- and methylthio-s-triazines in the with bacterial consortium for in situ bioremediation. On the basis
mixed culture are shown in Fig. 4. Degradation of methylthio-s- of this study, we will attempt to construct another charcoal mate-
triazines by the bacterial consortium, strain FJ1117YT and CD7, rial, which will include methylthio-s-triazines-degrading bacteria
was suppressed by the presence of sulfate (Fig. 3) as well as the that are not suppressed by external sulfur sources.
culture of strain FJ1117YT reported previously.9) However, Char-
Fig. 4. The expected metabolic pathways of chloro- and methylthio-s-triazines degraded by CD7 (strain CDB21) and strain FJ1117YT.
Simazine (R1, R2C2H5) and atrazine [R1C2H5, R2CH(CH3)2] were selected as chloro-s-triazines, and simetryn (R1, R2C2H5) and
dimethametryn [R1C2H5, R2CH(CH3)CH(CH3)2] were used as methylthio-s-triazines in this study.
270 K.-i. Yamazaki et al. Journal of Pesticide Science
ABSTRACT. The removal of crop residues for bio‐energy production reduces the formation of soil organic carbon (SOC) and
therefore can have negative impacts on soil fertility. Pyrolysis (thermoconversion of biomass under anaerobic conditions)
generates liquid or gaseous fuels and a char (biochar) recalcitrant against decomposition. Biochar can be used to increase
SOC and cycle nutrients back into agricultural fields. In this case, crop residues can be used as a potential energy source as
well as to sequester carbon (C) and improve soil quality. To evaluate the agronomic potential of biochar, we analyzed biochar
produced from poultry litter, peanut hulls, and pine chips produced at 400°C and 500°C with or without steam activation.
The C content of the biochar ranged from 40% in the poultry litter (PL) biochar to 78% in the pine chip (PC) biochar. The
total and Mehlich I extractable nutrient concentrations in the biochar were strongly influenced by feedstock. Feedstock
nutrients (P, K, Ca, Mg) were concentrated in the biochar and were significantly higher in the biochars produced at 500°C.
A large proportion of N was conserved in the biochar, ranging from 27.4% in the PL biochar to 89.6% in the PC biochar. The
amount of N conserved was inversely proportional to the feedstock N concentration. The cation exchange capacity was
significantly higher in biochar produced at lower temperature. The results indicate that, depending on feedstock, some
biochars have potential to serve as nutrient sources as well as sequester C.
Keywords. Agricultural residues, Biochar, Bioenergy, Black carbon, Carbon sequestration, Charcoal, Plant nutrition,
Pyrolysis, Soil fertility, Soil organic carbon.
P
yrolysis of crop residues to produce renewable ener‐ soil (Terra Preta) found throughout the lowland portion of the
gy is one option to reduce the use of fossil fuels. Py‐ Amazon Basin (Glaser et al., 2000). Research on tropical
rolysis generates biochar, oil, and gas products that soils indicates that charcoal amendments can increase and
can all be used as fuels (Ioannidou and Zabaniotou, sustain soil fertility (Steiner et al., 2007). The beneficial ef‐
2007). Pyrolytic biochar can also potentially be used as a low‐ fects appear to be related to alterations in soil physical, chem‐
cost sorbent (Ioannidou and Zabaniotou, 2007) or as a soil ical, and biological properties, such as reduced acidity
amendment to improve soil fertility and sequester carbon (Topoliantz et al., 2005), increased cation exchange capacity
(Lehmann et al., 2006; Steiner, 2007). Removal of crop resi‐ (CEC) (Cheng et al., 2008; Liang et al., 2006), enhanced ni‐
dues for energy production can have deleterious effects on trogen (N) retention (Lehmann et al., 2003; Steiner et al.,
soil organic carbon (SOC) and consequently on soil fertility 2008b), increased microbiological activity (Steiner et al.,
(Lal, 2004). Pyrolysis of crop residues with C returned to the 2008a), and increased mycorrhizal associations (Warnock et
soil in the form of biochar may help maintain or increase al., 2007). Research on the effect of wildfire charcoal in for‐
stable SOC pools and cycle nutrients back into agricultural est ecosystems indicates that it stimulates microbial activity
fields. Pyrolysis with biochar C sequestration may offer an (Pietikäinen et al., 2000) and influences nitrogen cycling
option to reduce the conflict between cultivating crops for (Berglund et al., 2004; DeLuca et al., 2006; Wardle et al.,
different purposes, e.g., energy vs. C sequestration or food. 1998). Research also indicates that charcoal is recalcitrant
There are several lines of evidence that charcoal plays an (Seiler and Crutzen, 1980), and it may persist for hundreds or
important role in soil fertility. Charcoal has been identified thousands of years.
as an important soil constituent in fertile Chernozems Charcoals produced from wildfire or traditional charcoal
(Schmitdt et al., 1999) and in anthropogenic enriched dark production may have different chemical and physical charac‐
teristics from pyrolytic biochars created under specific con‐
ditions for energy production. Both feedstock and pyrolysis
Submitted for review in August 2008 as manuscript number SW 7634; conditions such as temperature and carrier gas affect the
approved for publication by the Soil & Water Division of ASABE in chemical and physical characteristics of biochar (Antal and
November 2008. Grønli, 2003; Bansal et al., 1988; Benaddi et al., 2000; Guo
The authors are Julia W. Gaskin, Sustainable Agriculture Coordinator, and Rockstraw, 2007a; Strelko et al., 2002). Most of the liter‐
Christoph Steiner, Post‐Doctoral Associate, Keith Harris, Technician, K.
C. Das, Associate Professor, and Brian Bibens, Research Engineer, ature discusses high‐temperature biochars that are produced
Department of Biological and Agricultural Engineering, Driftmier at greater than 500°C or activated carbon typically produced
Engineering Center, University of Georgia, Athens, Georgia. at 800°C. As pyrolysis temperatures increase, volatile com‐
Corresponding author: Julia W. Gaskin, Department of Biological and pounds in the biochar matrix are lost, surface area and ash in‐
Agricultural Engineering, Driftmier Engineering Center, University of
crease, but surface functional groups that can provide
Georgia, Athens, GA 30602; phone: 706‐542‐1401; fax: 706‐542‐1886;
e‐mail: jgaskin@engr.uga.edu. exchange capacity decrease (Guo and Rockstraw, 2007a).
Table 1. Total element concentrations in the three agricultural feedstocks used for pyrolysis at 400°C and 500°C.
Values in g kg‐1 Values in mg kg‐1
Feedstock C N P K S Ca Mg Al Fe Na Cd Cr Cu Mn B Mo Ni Zn
Poultry litter (PL) 326 45.1 19.5 29.5 5.8 28.0 5.66 6.32 3.91 9.27 1.4 7.3 381 377.0 49.9 3.5 8.0 414
Peanut hulls (PN) 552 13.6 0.61 5.06 0.9 1.84 0.79 0.92 0.42 0.04 <1 2.0 36.5 44.0 15.2 15.6 1.5 20.2
Pine chips (PC) 571 0.9 0.08 0.59 0 0.75 0.21 0.03 0.13 0.04 <1 2.1 1.7 13.8 2.1 <1.0 <2.0 47.8
Table 2b. Means and standard errors for total micronutrient and selected element concentrations in poultry litter, peanut
hull, and pine chip biochars. Feedstock and temperature columns indicate significant differences (p < 0.05, n = 3).[a]
Poultry Litter (PL) Peanut Hulls (PN) Pine Chips (PC) Feedstock Temp.
400°C 500°C 400°C 500°C 400°C 500°C
Biochar SA Biochar SA Biochar SA Biochar SA Biochar SA Biochar SA
Al 9.87 8.12 13.02 14.25 2.40 2.33 2.73 2.81 0.07 0.05 0.07 0.06
(g kg‐1) ±1.36 ±1.59 ±0.36 ±1.97 ±0.07 ±0.16 ±0.05 ±0.13 ±0.01 ±0.005 ±0.01 ±0.008 PC, PN<PL 400<500
Fe 6.06 5.55 8.03 8.89 1.00 0.97 1.15 1.20 0.15 0.04 0.05 0.20
(g kg‐1) ±0.52 ±0.42 ±0.55 ±1.27 ±0.02 ±0.07 ±0.02 ±0.06 ±0.11 ±0.007 ±0.01 ±0.07 PC, PN<PL 400<500
Na 15.1 15.8 17.2 16.6 0.026 0.028 0.035 0.044 <0.014 0.053 0.013 0.075
(g kg‐1) ±0.31 ±1.37 ±1.02 ±1.12 ±0.001 ±0.006 ±0.004 ±0.005 ±0.004 ±0.032 ±0.002 ±0.054 PN, PC<PL
B 91.5 96.0 100 93.0 32.5 29.9 33.7 34.1 5.69 6.69 4.21 6.94
(mg kg‐1) ±3.16 ±8.25 ±0.31 ±3.98 ±1.57 ±2.87 ±0.27 ±1.15 ±0.30 ±0.21 ±0.62 ±1.33 PC<PN<PL
Cd 2.75 <2.65 <1.10 <1.35 <1.35
(mg kg‐1) ±0.73 ±0.83 <1 ±0.10 ±0.35 ±0.35 <1 <1 <1 <1 <1 <1
Cr 28.0 28.8 59.4 56.1 3.95 3.00 3.63 3.94 1.23 3.43 17.7
(mg kg‐1) ±4.1 ±5.2 ±3.3 ±4.5 ±0.31 ±0.57 ±0.31 ±0.16 <1 ±0.09 ±0.88 ±5.9 PN, PC<PL 400<500
Cu 805 880 1034 943 16 13 19 19 25 10 9 13
(mg kg‐1) ±23 ±49 ±68 ±81 ±0.60 ±1.27 ±0.50 ±1.84 ±7.03 ±6.18 ±2.34 ±5.57 PC, PN<PL 400<500
Mn 596 637 725 697 116 116 131 136 274 269 258 350
(mg kg‐1) ±5.6 ±37 ±29 ±46 ±2.3 ±8.0 ±2.3 ±5.7 ±9.3 ±7.8 ±30 ±4.0 PN<PC<PL 400<500
Mo 17.1 12.1 14.2 13.8 4.78 <4.11
(mg kg‐1) ±5.3 ±0.41 ±1.1 ±1.2 ±3.6 <1 <1 <1 <1 <1 <1 ±3.11 PC, PN<PL
Ni 13.6 19.5 20.3 29.1 <2.29 <2 <2 <10.4 <2 <2 <2.91 17.5
(mg kg‐1) ±0.00 ±3.7 ±1.1 ±8.4 ±0.29 ±0 ±0 ±8.0 ±0 ±0 ±0.55 ±14.7 PC, PN<PL
Zn 628 680 752 728 35 31 37 36 15 16 18 20
(mg kg‐1) ±12 ±41 ±28 ±50 ±2.2 ±2.9 ±2.1 ±0.00 ±1.1 ±0.7 ±0.6 ±2.4 PC, PN<PL 400<500
[a] SA = steam activation; < indicates mean contains results below the detection limit; ±0.00 indicates all results were near instrument detection limit.
biochar. Concentrations of plant nutrients in the feedstocks decreases the C content. Nitrogen, P, K, Ca, and Mg
generally followed the pattern of PC < PN < PL. Feedstock concentrations in the biochar were significantly different,
carbon concentrations had the opposite pattern, with PL < PN with PC < PN < PL (table2a). The concentration of the
< PC (table 1). micronutrients B, Cu, Fe, Mn, Na, and Zn were significantly
There were significant differences in C concentrations in higher in PL biochar (p < 0.05), but there were no differences
the biochar, with PL containing less C than the PN or PC detected between the PN and PC biochars except for Mn
biochar (table 2a). The nutrient‐rich poultry litter contains (table 2b). Concentrations of metals such as Al, Cr, Ni, and
relatively more minerals than the other feedstocks, which Mo were low. The PL biochar contained the highest
concentrations of these metals, as would be expected from In general, the PL biochar had a lower proportion of nutrients
the higher feedstock concentrations. Cadmium was below retained than the PN or the PC biochar (figs. 1c through 1f).
the detection limit in PC biochars and near or at the detection This may be due to a higher proportion of some of these
limits in PL and PN biochars (table 2b). elements retained in the aqueous/bio‐oil fraction in PL
The amount of N conserved ranged from 27.4% in the PL biochar (K. C. Das, 2007, unpublished data, University of
biochar to 89.6% in the PC biochar and was inversely Georgia, Athens, Ga.).
proportional to the feedstock N concentration (fig. 1b and The pattern of Mehlich I extractable concentrations was
table 1). The higher N losses seen from the PL were likely due similar to that of the total nutrient concentrations (tables 3a
to the volatilization of the poultry manure NH4-N and easily and 3b). There were significant differences in Mehlich I
decomposable N-containing organic compounds in the extractable P, K, Ca, and Mg concentrations, with PC < PN
manure, such as uric acid. In contrast, the low concentration < PL. There were differences by feedstock in the percentage
of N in the PC feedstock is likely to be incorporated into of the total nutrients that were Mehlich I extractable (figs. 1a
complex structures that are not easily volatilized. through 1f). Only 19% of the PL biochar P was Mehlich I
About 60% of the P in the PL and PC feedstock was extractable compared to over 40% in the PN biochar (400°C,
retained in the PL and PC biochar, while nearly 100% of the fig. 1c). About 90% of the PL biochar K was Mehlich I
P in the PN feedstock was retained in the PN biochar (fig. 1c). extractable compared to only 45% in the PN biochar (400°C,
Table 3b. Means and standard errors of the Mehlich I micronutrient and selected element concentrations in poultry litter,
peanut hull, and pine chip biochars. Feedstock and temperature columns indicate significant differences (p < 0.05, n = 3).[a]
Poultry Litter (PL) Peanut Hulls (PN) Pine Hips (PC) Feedstock Temp.
400°C 500°C 400°C 500°C 400°C 500°C
Biochar SA Biochar SA Biochar SA Biochar SA Biochar SA Biochar SA
Al 0.47 11.3 1.43 1.52 330 585 1129 1360 6.17 6.35 7.53 12.12
(g kg‐1) ±0.11 ±2.24 ±0.31 ±0.24 ±24 ±213 ±32 ±51 ±0.59 ±0.53 ±1.12 ±4.76 PL, PC<PN 400<500
Fe 0.66 3.16 0.06 0.19 140 142 197 221 3.72 4.58 14.6 33.3
(g kg‐1) ±0.21 ±0.08 ±0.007 n=1 ±2.2 ±18 ±3.8 ±11 ±0.26 ±0.19 ±2.89 ±8.39 PL, PC<PN 400<500
Na 9.57 7.08 6.98 7.24 0.02 0.02 0.02 0.03 0.03 0.03 0.03 0.08
(g kg‐1) ±0.19 ±1.61 ±0.43 ±0.07 ±0.001 ±0.002 ±0.58 ±0.002 ±0.002 ±0.002 ±0.005 ±0.037 PN, PC<PL
B 16.7 18.8 18.67 20.4 4.20 4.96 3.97 5.84 0.45 0.41 0.52 1.15
(mg kg‐1) ±1.59 ±2.05 ±0.85 ±0.59 ±0.12 ±1.08 ±0.22 ±0.66 ±0.04 ±0.07 ±0.07 ±0.49 PC<PN<PL
Cr 0.19 0.19 0.14 0.11 0.41 0.52
(mg kg‐1) ±0.03 ±0.02 ±0.01 ±0.01 <0.04 <0.04 ±0.04 ±0.03 <0.06 <0.06 <0.06 <0.06
Cu 0.40 0.29 <0.08 <0.05 0.67 <0.59 <0.04 6.55 2.48 2.70 3.82
(mg kg‐1) ±0.06 ±0.08 ±0.02 ±0.005 ±0.04 ±0.32 ±0.001 <0.04 ±2.18 ±0.68 ±0.89 ±3.34 PL, PN<PC
Mn 7.69 8.64 6.75 5.17 24.7 21.2 14.4 16.3 22.6 25.2 24.1 36.2
(mg kg‐1) ±1.23 ±1.28 ±1.03 ±0.43 ±0.70 ±2.33 ±0.45 ±0.71 ±2.61 ±3.79 ±6.67 ±12.5 PL<PN<PC
Mo 0.87 1.11 1.42 1.94 0.15 0.25 0.11 0.65
(mg kg‐1) ±0.19 ±0.22 ±0.14 ±0.19 <0.04 <0.04 <0.04 <0.04 ±0.002 ±0.06 ±0.03 ±0.35
Ni
(mg kg‐1) <0.08 <0.08 <0.08 <0.08 <0.08 <0.08 <0.08 <0.08 <0.2 <0.2 <0.2 <0.2
Zn 0.06 0.30 0.05 10.51 7.36 5.58 6.30 2.20 2.31 1.36 3.66
(mg kg‐1) ±0.01 ±0.02 ±0.07 <0.04 ±1.22 ±0.59 ±0.26 ±0.45 ±0.17 ±0.21 ±0.26 ±1.17 PL<PC<PN
[a] SA = steam activation; < indicates mean contains results below the detection limit.
fig. 1d). Manganese and Zn concentrations were significantly potential for different biomass sources and production
lower in the PL biochar than the PC or PN biochars. Copper, techniques to supply plant‐available nutrients. The
Al, and Fe was also lower in the PL biochar compared to the extraction has not been calibrated for biochar and may not
PN biochar. These patterns are the reverse of that seen in the reflect actual plant‐available nutrient concentrations.
feedstock or the total element concentrations in the biochars. However, data from a greenhouse trial using pine chip and
If pyrolysis can reduce P and other metal availability in peanut hull biochar amendment of three different Ultisols
poultry litter, it may reduce some of the environmental (Speir, 2008) and from a field trial with the same biochars
concerns associated with land application of poultry litter. (Gaskin et al., 2007) indicate an increase in Mehlich I K and
These results should be interpreted with caution. The Mg in soils amended with peanut hull biochar. The increased
Mehlich I extraction, which is a weak double acid extraction, Mehlich I K in the soil was reflected in an increase of these
may not have been strong enough to remove these acid‐ nutrients in corn tissue (Zea mays) in the field trial.
soluble cations under the high pH conditions found in the PL The pH and CEC of the biochars were also significantly
biochar. influenced by feedstock (table 2a). All the biochars were
The Mehlich I extraction was developed for acidic soils in basic, with the highest pH seen in the PN biochar. Tryon
the southeastern U.S. with low CEC or base saturation (Kuo, (1948) reported increased soil pH with the addition of pine
1996), and it is the standard extraction used for plant‐ and hardwood charcoal. He attributed the greater pH increase
available nutrients and fertilizer recommendations in seen in the hardwood charcoal treatment to the higher ash
Alabama, Georgia, Florida, South Carolina, Tennessee, and content, in particular to the hydrolysis of salts of Ca, K, and
Virginia. In this study, Mehlich I extractable element Mg in the presence of water. In this study, PC biochar had
concentrations were used as an index to compare the both the lowest total concentrations of these cations and the
lowest pH, which would support Tyron's hypothesis; Services Laboratory, unpublished data). Small amounts of
however, the pH of PL biochar was similar to the PN biochar this NH4-N may remain trapped, or microbes may have
although it contained higher concentrations of total Ca, K, mineralized nitrogen‐containing organic compounds in the
and Mg than PN biochar (table 2). biochar. Das et al. (2008) found that the liquid products
Higher CEC was associated with higher concentrations of obtained from poultry litter pyrolysis enhanced microbial
minerals in the feedstock. Mészáros et al. (2007) growth in well water and concluded that N-heterocyclic
hypothesized that K, Mg, Na, and P in the biomass may compounds derived from proteins were responsible for that
catalyze the formation of oxygen groups on the biochar increase. A small fraction of these compounds may be
surface at low pyrolysis temperatures. Oxygen groups such present in the biochars.
as carboxyls, lactones, and phenols could contribute to the
presence of negative surface charges (Boehm, 1994). INFLUENCE OF PYROLYSIS TEMPERATURE
Dissolved C concentrations were very low (table 4). The average conversion ratio (biochar weight / feedstock
Feedstock had a significant effect on DC in the biochar weight) was 33.2%. Biochar yield decreased with increased
leachate, with PC < PN < PL. Dissolved inorganic C was also pyrolysis temperature, and except for N, nutrient
affected by feedstock, with PC < PN < PL. The PL biochar concentrations were higher in the biochar produced at 500°C
had a higher proportion of DOC than PC or PN biochars. The (tables 2a andb). Due to the wide range of initial nutrient
PL feedstock is a combination of wood chip (typically pine) concentrations in the feedstock, there were significant
bedding and poultry manure. The manure may contribute to interactions between feedstock and temperature for total N,
higher DOC leached from the PL biochar. P, Mg, Mn, Cu, Fe, Zn, and Al (p < 0.05).
DOC plays an important role in many soil processes, As noted earlier, N was conserved in the biochar (fig. 1b).
including serving as an energy source for the microbial After forest fires, on average, only 3% of the N in the biomass
community and reacting with other soil solution components is found in ash, which contains black carbon or biochar
(Sposito, 1989). Biochars are known to contain condensed (Giardina et al., 2000). Almendros et al. (2003) found C and
volatile compounds. These compounds are either lost to the N enrichment in charred residues during thermal
gaseous or liquid phase or undergo further reactions to form transformation of peat organic matter. Nitrogen was
secondary char at high temperatures (Antal and Grønli, incorporated into structures resistant to heating at moderate
2003). Garcia‐Perez et al. (2007) identified water‐soluble thermal oxidation by aromatization and formation of
compounds from pyrolysis of lignin materials to contain heterocyclic N (Almendros et al., 2003). Studies of wildfire
mono‐ and oligo‐sugars, formic and aecetic acids, as well as effects on biomass composition indicate that N begins to
methanol, hydroxyl‐acetaaldehyde, and 1‐hydroxyl‐2‐ volatilize at 200°C, and above 500°C half of the N in organic
propanone. Schnitzer et al. (2007) identified numerous matter is lost to the atmosphere. Our study indicated that a
organic compounds in the light and heavy fractions of poultry relatively high proportion of the feedstock N was conserved
litter pyrolyzed at 330°C, including N-heterocyclics, at low pyrolysis temperatures, and as expected more N was
substituted furans, phenol and substituted phenols, benzenes retained in the biochar at 400°C compared to 500°C (fig. 1b).
and substituted benzenes, as well as aliphatic C chains. It is Knicker et al. (2005) has shown that fire and carbonization
likely that some of these compounds remain trapped in the can increase the N content of SOC, but the alterations in
biochar pore structure, but few of these compounds appear to chemical structure have long‐term consequences for N
be immediately water soluble. availability (Knicker and Skjemstad, 2000). Field trials of PN
Ammonium‐nitrogen in the biochar leachate was also and PC biochar as a soil amendment with corn (Zea mays)
found in very low concentrations (table 4). No NO3-N was indicate that PN biochar N is not plant available (Gaskin et al.,
detected in any of the leachates. The NH4-N concentrations 2007). However, Tagoe et al. (2008) studied N recovery of
were highest in the leachate from the PL biochar. Fresh 15N‐labeled chicken manure and did not find differences in N
poultry litter typically contains about 2.8 g NH4-N kg-1 availability between carbonized and dried chicken manure.
(University of Georgia Agricultural and Environmental
CONCLUSIONS
Pyrolytic biochar has the potential to be used in
agricultural production to sequester carbon and serve as a
fertilizer. Although pyrolysis conditions are known to affect
the chemical and physical characteristics of biochar, at the
relatively low pyrolysis temperatures used in this study,
feedstock characteristics had the greatest influence on key
agricultural characteristics. Carbon concentrations in the
biochars decreased with increasing mineral content of the
Figure 2. Representative relationship of the ratio of nutrient (K) in the
biochar to feedstock and conversion efficiency for pine chip, peanut hull, feedstock. Little DC was leachable from the fresh biochar. A
and poultry litter biochars. Solid circles represent means, and bars high proportion of the feedstock N was conserved in the
indicate standard errors. biochar; however, the N may not be plant available. Nutrients
such as P, K, and Ca are extractable with a weak double acid
The total concentration of other elements (P, K, Ca, and extractant and may be plant available.
Mg) significantly increased with increasing volatization The higher pyrolysis temperature increased nutrient
losses of C, H, O, and N (tables 2a and 2b). Potassium is concentrations, except for N, but decreased CEC. Recent
representative of the nutrient concentration seen (fig. 2). literature has shown that natural long‐term oxidation of
Potassium and P vaporize at temperatures above 760°C, S biochar in the soil increases the amount of negative charges
and Na need temperatures above 800°C, and Mg and Ca are on the biochar surface (Cheng et al., 2008). Development and
lost only at temperatures above 1107°C and 1240°C, optimization of pyrolysis and post‐production treatments to
respectively (Lide, 2004, reviewed by Knicker, 2007). There increase CEC or available nutrients is important in order to
was a significant interaction between temperature and increase the immediate benefits of biochar applications in
feedstock for Mehlich I extractable concentrations of these agriculture.
elements (p = 0.05). At the low nutrient concentrations seen
in the PC biochar, temperature appeared to have little effect. ACKNOWLEDGEMENTS
In the PN and PL biochars, Mehlich I extractable nutrients This work was conducted with funding from the State of
tended to decrease with increasing temperature. Mehlich I Georgia and the U.S. Department of Energy. We wish to
extractable Al and Fe were significantly increased in the thank Dr. Jim Kastner for his helpful comments on various
500°C biochar (table 3b). ideas in the manuscript, and Mr. Roger Hilten for assistance
with this project.
Abstract: Char produced from the pyrolysis of biomass has potential as an agricultural amendment for increasing agricultural productivity in the
infertile, low C soils of the southeastern United States, but it is unclear if the chars produced by pyrolysis plants will function in soils
similar to the charcoal in Terra Preta. Recent work in characterizing pyrolysis char indicates that the feedstock, temperature, and
carrier gas has a strong influence on important characteristics for agricultural production, such as available nutrients, cation exchange
capacity, and mineralization rates. Preliminary data indicate pyrolysis char may increase CEC, sorbs P, and serves as a source of plant
available K. Nitrogen mineralization data and first growing season field trials with corn (Zea mays) indicate although some
mineralization may occur, N in high N char (2%) is not readily available. A better understanding of char effects on soil processes is
needed.
Keywords: char, Ultisols, agricultural amendment, nutrients, nitrogen, mineralization, cation exchange capacity, phosphorus sorption
1. INTRODUCTION
Char produced from the pyrolysis of biomass has potential as an agricultural amendment in low fertility soils. Much
of the interest in its potential use as an agricultural amendment has been stimulated by research discussed in this book and
the previous volumes on the role of charcoal in Terra Preta soils. Results from studies conducted in South American and
African tropics on acidic, highly-weathered Oxisols with low organic carbon, cation exchange capacity, and base
saturation indicates that addition of charcoal has significantly influenced nutrient cycling, soil biology, and crop
productivity (Glaser et al. 2002; Lehmann and Rondon 2006; Oguntunde et al. 2004). Increased yields and biomass have
been reported for various legumes (Iswaran et al. 1980; Lehman et al. 2003; Topoliantz et al. 2005) and for corn
(Lehmann and Rondon 2006; Oguntunde et al. 2004). Increased productivity may be related to available nutrients (Glaser
et al. 2002; Lehman et al. 2003; Steiner et al. 2007), or increases in pH (Topoliantz et al. 2005; Steiner et al. 2007), and
cation exchange capacity (CEC)(Steiner et al. 2007, Liang et al. 2006), as well as changes in water relations and soil
biology (Glaser et al. 2002; Steiner et al. 2004). Although most studies report increased plant productivity with charcoal
addition, plant biomass decreases have been observed, particularly at high application rates (Glaser et al. 2002). These
responses could be related to nitrogen immobilization through high C:N ratios and sorption of NH4-N and NO3-
N(Lehmann and Rondon 2006).
The southeastern United States is an important agricultural area. The state of Georgia alone has approximately 4.3
million hectares of corn (Zea mays), soybean (Glycine max), cotton (Gossypium hirsutum), and peanuts (Arachis
hypogaea) in production and 9.6 million hectares of forestland largely in loblolly pine (Pinus taeda) production (USDA
2002; Georgia Forestry Association 2007). The growing interest in biofuels is increasing demands on row crop
production and may also increase demand on forestlands. The Ultisols of the southeastern United States are similar to
tropical Oxisols with low organic carbon contents of less than 1%, low cation exchange capacities of approximately 5
cmol kg-1, and low base saturation of usually less than 30% (Perkins 1987). Char produced as a byproduct of energy
production through pyrolysis may provide an opportunity to increase the productivity of southeastern soils, similar to the
way charcoal functions in Terra Preta. However, because char characteristics vary with feedstock and pyrolysis
conditions (Harris et al. 2006; Antal and Gronli 2003), a better understanding of the influence of these factors on char
characterisitics and the effect of different chars on soil processes in the southeastern United States is needed.
Char or charcoal corresponds to black carbons that result from the incomplete combustion of biomass. Black carbon
consists of graphite-like planes (graphene layers) that show varying degrees of disorientation. The resulting spaces
between these planes constitute porosity.
The capacity of char to remove impurities from solutions and gases has been known for many centuries. This is due to
the porous nature of the material (Barkauskas 2002) and to the surface chemical properties including the type and number
of functional groups (Stoeckli et al. 2004). Charcoal has chemical reactivity due to the existence of unsaturated valence
(active sites) at the edges of the aromatic planes. The ratio of these active sites in relation to the inert carbon atoms within
1
the graphene layers increases as the surface area increases. Heteroatoms, such as oxygen, hydrogen or nitrogen also have a
strong influence on the mechanisms of the adsorption process. Oxygen is the most important heteroatom and is part of
chemical groups that have both Lewis base properties such as chromene and pyrone or acidic properties such as
anhydrides, lactones, lactols, phenols, carbonyls, and carboxyls. The presence and quantity of these groups affect the
capacity of char to add to the cation or anion exchange capacity of the soil and other soil productivity properties.
Charcoals are known to sorb cations (Lima and Marshall 2005a) and also anions when basic surface oxides are present
due to exposure to the atmosphere (Boehm, 1994). These sorption capacities may create the potential for char to retain
needed nutrients in the low exchange capacity soils of the southeastern United States.
2.1 Feedstocks
The mineral content of the char depends upon the nature of the feedstock and can influence the surface chemistry of
charcoal by interaction with electrons of the aromatic rings and through electron paramagnetism. (Benaddi et al. 2000).
Ash complicates interpretation of surface phenomena of carbon. Ash solubility in water is variable, making the analysis
of surface groups difficult at higher ash concentrations. Insoluble metal oxides involved in the charge development on the
carbon surface become charged in aqueous suspension, and are considered part of the active surface sites.
Feedstock particle size also affects char yield from pyrolysis. At low pyrolysis temperature, larger particle sizes favor
longer inter-pore residence time for volatiles increasing yield (Antal and Gronli, 2003).
2.3 Comparison between traditional two-step pyrolysis and activation with 1-step steam pyrolysis
Typically chars produced at temperatures around 400 to 600 oC do not have the well developed surface areas or
adsorbent properties of activated carbons because of tars deposited on the solid surface that restrict pore structures.
Steam activation at temperatures between 800 and 1,100 oC physically removes these residues and opens pores. After
activation, chars have higher surface area, adsorption capacity and pore size distribution (Gregova et al. 1994; Alaya et al.
2000).
The combination of this two-step process into a single step, which involves pyrolyzing under steam conditions, may
increase surface area and increase adsorbent properties, and requires less energy and less time. Steam pyrolysis at low
temperatures (600 oC) has been shown to increase micropores with the ratio of micropore volume to total pore volume
approaching 95% (Alaya et al. 2000). These authors suggest that steam enhances the evolution of volatile molecules at
2
lower temperatures and prevents the cracking of volatiles. In addition, gasification (conversion of solids to gases) is
induced much earlier (600 oC compared to 800 to 900 oC in non-steam environments) and results a more porous carbon
skeleton. Chars produced at lower temperatures with steam may have a more active surface chemistry; however, the
literature is not clear about the impacts of one-step processing on nutrient properties and surface chemistry.
Based on available literature on char and activated carbons, it appears that chars produced at low pyrolysis
temperatures with steam may hold the greatest promise for agricultural use due to lower production cost, higher surface
functional groups for sorption, and a more dense char product.
9000
8000
7000
6000
K mg kg-1
5000 PC
4000 HW
3000 PN
2000
1000
0
380 400 420
Tem perature
Figure 1. Total nutrients in char produced from pine chips (PC), hardwoods (HW), and peanut hulls (PN) pyrolized with steam at three different
temperatures.
At these low pyrolysis temperatures, the total N concentration in the char was similar to that of the initial feedstock
(Table 1). Total N concentration in the PL and PN char was high at 3.7% and 2%, respectively. The PL char
concentration was higher than that reported for active carbon produced from turkey litter (1.12%) although the N
concentration of the turkey litter feedstock was similar at 3.84%(Lima and Marshall 2005b). The turkey litter active
carbon was produced at 700 oC and activated with steam at 800 oC, which may have volatilized more N. The N
concentrations in PC and HW char were similar to those reported for pinewood (0.11%) and oak board (0.18%) char by
Antal and Gronli (2003).
3
Although the N concnetration of the PN char is potentially high enough to offer a substantial nitrogen input and the
C:N ratio is relatively low (33, Table 1), the N does not appear to be readily available. Nitrogen mineralization was very
low in incubations (24-days at 25 o C, 55% water filled pore space) of infertile, low C Tifton soils (fine-loamy, siliceous,
thermic Plinthic Kandiudults) amended with PN and PC chars at 11 and 22 Mg ha-1 equivalent rate (Table 2). These PN
and PC chars were produced in a pilot scale pyrolysis unit at 400 oC with steam. Peanut hull char C and N concentrations
were 72.85and 1.90%, respectively, and PC char C and N were 76.99 and 0.17%, respectively. There was no statistical
difference in NH4-N concentrations between the control and char amended soils (p=0.05). There was a trend for higher
NO3-N concentrations in the PN amended soils, but only the PN 11 Mg ha-1 rate was statistically different from the
control.
Table 2. Mean change (final –initial) in ammonium- and nitrate-nitrogen concentrations with standard deviations in Tifton soils amended with peanut
hull (PN) and pine chip (PC) char at 11 and 22 Mg ha –1 and incubated for 24 days. Analysis of variance with mean separation by Tukey-Kramer
Multiple Comparison test. Letters within the same column indicate statistical difference at the p=0.05 level.
---------------mg kg-1--------------
PN 11 4 1.49 +/- 0.24 5.53 +/- 0.65b
PN 22 4 0.94 +/- 0.78 5.08 +/- 0.62a
PC 11 4 1.19 +/- 0.36 3.62 +/- 0.51a
PC 22 4 1.44 +/- 0.26 4.41 +/- 0.16a
Control 4 1.37 +/- 0.38 3.26 +/- 1.66
We saw similar indications that N in the high N char was not plant available in the first year of field trials on similar
Tifton soils with irrigated corn (Zea mays, Gaskin et al. 2006). Peanut hull char was incorporated to a depth of 15 cm in
microplots (1.8 x 2.2 m) at rates of 0, 11 and 22 Mg ha-1 in a factorial combination with two rates of nitrogen fertilizer (0
and 213 kg N ha-1) surface applied as ammonium nitrate. Tissue samples at the earleaf stage during the first growing
season only showed a significant effect (p=<0.0001) due to N fertilizer. The mean N tissue concentration in the PN
char/no N fertilizer treatments were similar to the control (1.40%) and had average N concentrations averaging 1.13% for
the PN 11 and 1.52% for the PN 22 treatment. Nitrogen tissue concentrations in the N fertilized treatments averaged
2.91%. At the p=0.05 level, there was a significant effect due to N fertilizer for both grain yield and stover (p= <0.0001;
Figure 2), but no significant effect due to char rate for grain (p=0.7197). There was a significant effect of char rate for
stover (p=0.0241). The interaction between char and fertilizer was only significant for the stover (p=0.0145). These
preliminary data indicate, although some N may be mineralizing, the N in the PN char is not readily available to
microorganisms in the short–term (24-days) and is not highly plant available over a growing season (approximately 4
months).
Grain Stover
18
16
14
12
Mg ha-1
10
8
6
4
2
0
22
11
22
11
PN F
PN F
F
l
l
er
er
ro
ro
+
+
PN
PN
liz
liz
PN
PN
nt
nt
22
11
22
11
rti
rti
Co
Co
PN
PN
Fe
Fe
Treatm ent
Figure 2. Corn grain yield and stover (dry wt basis) from Tifton soil plots amended with peanut hull (PN) biochar. Fertilizer – N fertilizer check,
PN22+F- PN char at 22 Mg ha-1 + N fertilizer, PN11+F- PN char at 11 Mg ha-1 + N fertilizer, PN22- PN char at 22 Mg ha-1, PN11 char at 11 Mg ha-1,
Control- no amendment or N fertilizer.
4
Although N in the char does not appear to be readily available, the char may serve as a source for other nutrients,
particularly K. Mehlich I K at the end of the first growing season was higher in the PN char amended plots than the
control (Table 3).
Table 3. Mehlich I K in Tifton soil amended with peanut hull (PN) char at 11 and 22 Mg ha-1. Analysis of variance with mean separation by Tukey-
Kramer Mulitple Comparision Test. Letters within rows indicate statistical difference at p=0.05 level.
Table 4. Mean cation exchange capacity and standard deviation in peanut hull(PN), pine chip (PC) and hardwood (HW) chars produced at three
pyrolysis temperatures with steam.
Temperature
Feedstock 380° C 400° C 420° C
---------------------------------cmol kg-1------------------------------------
PN 36.7+/-0.76 (n=4) 44.0+/-0.35 (n=2) 28.0+/-5.26 (n=4)
PC 18.6+/-1.34 (n=3) 27.0+/-0.60 (n=2) 16.5+/-2.42 (n=4)
HW 22.6+/-0.04 (n=2) 22.9+/-3.21 (n=2) 14.1+/-0.34 (n=2)
5
160
140
120
P adsorbed (mg kg-1)
100
80
60
Soil + PC
40
Soil + PN
20
Soil alone
0
0 20 40 60 80 100 120
Figure 3. Phosphorus adsorption isotherm form a Tifton soil amended with pine chips (PC), and peanut hull (PN) chars pyrolyzed at 420 oC with
steam at 0.05 g char g-1 soil .
4. SUMMARY
Soils in the southeastern United States are typically have low C, CEC, and base saturation. Studies of Terra Preta soils
show charcoal has an important influence on these soils productivity and reviews of the activated carbon literature
illuminate some of the physical and chemical mechanisms that could influence soil productivity with char addition.
Pyrolysis chars may have the potential to supply nutrients, sorb cations and anions. The literature and our data indicate
pyrolysis conditions and the feedstock have considerable effects on char characteristics. Our studies on feedstocks
commonly available in the southeastern United States indicate had CECs that potentially increase the ability of low C
loamy sands to retain nutrients. Some chars also have the potential to increase P sorption. It is unknown at this point if
there would be subsequent desorption of P by char and what affect this may have on crops.
Preliminary studies indicate that N from chars with a relatively high N content such as peanut hulls was not readily
bioavailable during the first year of cropping, but some chars contain mineral nutrients such as K that are available to
crops. Our preliminary work indicates char addition may have potential agricultural benefits, but a better understanding
of how char from various feedstocks and produced under different pyrolysis conditions changes soil processes and crop
response is needed.
5. REFERENCES
Alaya, M.N., B.S. Girgi, and W.E. Mourad. (2000). Activated carbon from some agricultural wastes under action of one-
step steam pyrolysis. Journal of Porous Materials 7: 509-517.
Antal, M.J. and M. Gronli. (2003). The art, science, and technology of charcoal production. Industrial and Engineering
Chemistry Research 42:1619-1640.
Asada, T., Ishihara, S., Yamame, T., Toba, A., Yamada, A., and Oikawa, K. 2002. Science of bamboo charcoal: study on
carbonizing temperature of bamboo charcoal and removal capability of harmful gases. Journal of Health Science
48[6], 473-479.
Bansal, R.C., J. Donnet, F. Stoeckli. 1988. Active Carbon. Marcel Dekker, Inc. New York. 482 pp.
Barkauskas, J. (2002). Functional groups on the surface of activated carbons. Part A. Investigation by means of proton
affinity distribution. Chemine Technologia, 24 (3).
Benaddi, H., T. J. Bandosz, J. Jagiello, J. A. Schwarz, J. N. Rouzaud, D. Legras, and F. Beguin. 2000. Surface
functionality and porosity of activated carbons obtained from chemical activation of wood. Carbon 38(5):669-674.
Boehm, H.P. (1994). Some aspects of the surface chemistry of carbon balcks and other carbons. Carbon, 32 (5), pp. 759-
769.
Gaskin, J., L. Morris, D. Lee, R. Adolphson, K. Harris, and K.C. Das. (2006). Effect of pyrolysis char on corn growth and
loamy sand soil characteristics. Abstracts of American Society of Agronomy, Crop Science Society of America, and
Soil Science Society of America International Annual Meetings. Nov. 12-16, 2006. Indianapolis, IN.
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Georgia Forestry Commission. (2007). Georgia Facts. http://www.gfagrow.org/facts.asp
Giles, C.H., MacEwan, T.H., Nakhwa, S.N., and Smith, D. 1960. Studies in adsorption. isotherms and its use in
diagnosis of adsorption mechanisms and in measurements of specific surface areas of solids. J. Chem.
Soc., London, 3973-3993.
Glaser, B., J. Lehmann, and W. Zech. (2002). Ameliorating physical and chemical properties of highly weathered soils in
the tropics with charcoal – a review. Biology and Fertility of Soils 35:219-230
Gregova, K., N. Petrov, and S. Eser. (1994). Adsorption properties and microstructure of activate carbons produced from
agricultural by-products by steam pyrolysis. Carbon 32(4):693-702.
Guo, Y. and D. A. Rockstraw. 2007. Physicochemical properties of carbons prepared from pecan shell by phosphoric acid
activation. Bioresource Technology, 98 (8), 1513-1521
Harris, K., J.W. Gaskin, L.S. Sonon, and K.C. Das. (2006). Characterization of pyrolysis char for use as an agricultural
soil amendment. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of
America International Annual Meetings. Nov. 12-16, 2006. Indianapolis, IN.
Iswaran, V., K.S. Jauhri, and A. Sen. (1980). Effect of charcoal, coal and peat on the yield of moong, soybean and pea.
Soil Biol. Biochem. 12:191-192.
Iyobe, T., T. Asada, K. Kawata, and K. Oikawa. (2004). Comparison of removal efficiencies for ammonia and amine
gases between woody charcoal and activated carbon. Journal of Health Science 50[2], 148-153.
Liang, B., J. Lehman, D. Solomon, J. Kinyangi, J. Grossman, B. O’Neill, J.O. Skjemstad, J. Thies, F.J. Luizao, J.
Peterson, and E.G. Neves. (2006). Balck carbon increases cation exchange capacity on soils. Soil Sci. Soc. Am. J.
70:1719-1730.
Lehman, J. and M. Rondon. (2006). Bio-char soil management on highly weathered soils in the humid tropics. In:
Uphoff, N., A.S. Ball, E. Fernandes, H. Herren, O.Husson, M.Lang, C. Palm, J. Pretty, P. Sanchez, N. Sanginga,
and J. Theis (eds). Biological Approaches to Sustainable Soil Systems. CRC Taylor and Francis, Boca Raton, FL.
Lehman, J. J. Pereira da Silva, Jr., C. Steiner, T. Nehls, W. Zech, and B Glaser. (2003). Nutrient availability and leachng
in an archealogical Ahtrosol and a Ferrasol of the Central Amazon basin: fertilizer, manure and charcoal
amendments. Plant and Soil 249:343-357.
Lima, I. and W.E. Marshall. 2005a. Adsorption of selected environmentally important metals by poultry manure-based
granular activated carbons. Journal of Chem Technol Biotechnol 80:1054-1061.
Lima, I and W.E. Marshall. 2005. Utilization of turkey manure as granular activated carbon: physical, chemical and
adsorptive properties. Waste Management 25:726-732.
McBride, M.B. 1994. Environmental Chemistry of Soils. Oxford University Press, 406 pp.
Oguntunde, P.G., M. Fosu, A.E. Ajayi, N. van de Giesen. (2004) Effects of charcoal production on maize yields, chemical
properties and texture of soil. Biol. Fertil. Soils 39:295-299.
Perkins, H.,F. (1987). Characterization Data for Selected Georgia Soils. The Georgia Agricultural Experiments Stations,
College of Agriculture, The University of Georgia. Athens, GA. Special Publication 43.
Sonon, L. K. Harris, J. Gaskin, and K Das. (2006). Phosphorus sorption characteristics of Tifton soil amended with
pyrolysis-derived chars. Abstracts of American Society of Agronomy, Crop Science Society of America, and Soil
Science Society of America International Annual Meetings. Nov. 12-16, 2006. Indianapolis, IN.
Sposito, G. (1989). The Chemistry of Soils. Oxford University Press. NY, USA.
Stoeckli, F., A. Guillot, and A.M. Slasli. (2004). Specific and non-specific interactions between ammonia and activated
carbons. Carbon 42 (8-9): 1619-1624.
Strelko, V., D.J. Malik, and M. Streat. (2002). Characterisation of the surface of oxidized carbon adsorbents. Carbon
40(1):95-104.
Steiner, C., W.G. Teixeira, J. Lehman, T. Nehls, J.L. Vasconcelos de Macedo, W. E. H. Blum, W. Zech. (2007). Lang
term effects of manure, charcoal and mineral fertilization on crop production and fertility on a highly weathered
Central Amazonian upland soil. Plant Soil 291(1-2):275-290.
Steiner, C. W.G. Teixeira, J. Lehman, and W. Zech. (2004). Microbial response to charcoal amendments of highly
weathered soils and Amazonian dark earths in Central Amazonia – Preliminary results. In: B. Glaser and W.I.
Woods (eds). Amazonian Dark Earths: Explorations in Space and Time. Springer-Verlag, New York, NY. pp. 195-
212.
Sumner, M.E. and W.P. Miller. (1996). Cation exchange capacity and exchange coefficients. In: Methods of Soil
Analysis. Part 3. Chemical Methods. Soil Sci. Soc. Am. and Am. Soc. Agron. SSSA Book Series No. 5.
Topoliantz, S., J-F. Ponge, and S. Ballof. (2005). Manioc peel and charcoal: a potential organic amendment for
sustainable soil fertility in the tropics. Biol. Fertil. Soils 41:15-21.
USDA. (2002). Census of Agriculture. 29 May 2007. <http://www.nass.gov/Data_and_Statistics/Quick_Stats/>
7
Distributed Hydrogen Production with Profitable Carbon Sequestration: A Novel Integrated Sustainable System for Clean
Fossil Fuel Emissions and a Bridge to the New Hydrogen Economy and Global Socio-Economic Stability
Danny M. Day, Eprida, Inc., 6300 Powers Ferry, Suite 307, Atlanta, Georgia
danny.day AT eprida.com, 404-228-8687
Robert J. Evans, National Renewable Energy Laboratory, Golden, Co
James W. Lee, Oak Ridge National Laboratory, Oak Ridge, TN
Introduction and Abstract
Carbon dioxide (CO2) emissions from fossil fuel combustion directly contribute to ris ing atmospheric CO2 levels, which in
turn are likely linked to global climate change. The need for efficient and economical technologies to rapidly sequester point
source production of carbon dioxide has become both an urgent and widespread technical need. The significant adoption of
any mitigation technology requires a measurable return to end-users. An example is coupling enhanced oil recovery (EOR)
with deep well injection of CO2, though to be economically viable, the carbon dioxide source must be co-located with the oil
fields. We propose an integrated sequestration approach in which agricultural waste products are used to produce hydrogen, a
renewable fuel, and a carbon sequestering soil amendment (char) as a valuable co-product. The dual function char,
derivitized with ammonium bicarbonate (2NH4 HCO3 ) (“ABC”) obtained from treating power plant CO2 emissions, acts both
as an enriched carbon, organic slow release fertilizer and a long-lived carbon storage medium in soils or ECOSS™.
?To verify a hydrogen co-product could be produced that would offer sufficient value for high volume application
?Test a simply production process that would allow the co-product to be produced from the exhaust of fossil fuel
combustion,
?Analyze the material for characteristics needed of a large volume co-product.
The ammonium bicarbonate technology, developed through the collaboration of Oak Ridge National Laboratory (ORNL), the
National Renewable Energy Laboratory (NREL) and Eprida Scientific Carbons, Inc. (E-SCI), operates at ambient temperature
and pressure and does not require carbon dioxide separation or energy intensive compression. Chars generated from
agricultural waste pyrolysis have been derivitized with the ammonium bicarbonate. This research provides results that point
toward the utilization as a time-release fertilizer while concurrently sequestering stable charcoal in soils and producing an
excess of hydrogen. This hydrogen manufacturing and sequestration strategy utilizes the largest existing market for hydrogen
(i.e. the production of fertilizer) and leverages the existing farm fertilizer infrastructure to restore soil carbon lost by erosion
and extensive tillage. An ancillary benefit of this process is the accrual of carbon credits from capturing power plant
emissions, producing a long-lived carbon soil amendment, and enhancing plant growth. If this integrated strategy ultimately
proves successful, then the agricultural sector can play an inte gral role in developing the hydrogen economy and restore soil
carbon, sequestering vast amounts of carbon, while increasing available nitrogen and sustained natural sequestration will
occur through enhanced plant growth. Implementation could allow hydrogen production to work synergistically with fossil
fuel emission reductions. A global economic stimulus is possible through profitable sequestration, increased farm
productivity, local energy production, rural income opportunities, small business development and offer hope for a positive
and sustainable future.
1
Step 1. Hydrogen Production Leveraging Photosynthesis
Extract Hydrogen From Organic Matter Catalytic Steam
Reforming
60% H2
20% CO2
7% CO
3% CH4
100-Hour Field Demonstration of
Hydrogen From Biomass Catalytic Steam
Reforming (August 2002)
Charcoal Background
? Forest fires have been sequestering carbon in the
soil in as charcoal for billions of years
? The half-life of charcoal in the soil is measured in
1000’s of years (Skjemstad)
? Charcoal even in weathering environments can be
found as old as 11,000 years old (Gavin)
3
Current Research
The images above were provided for this poster by Christoph Pyrogenic Carbon Benefits
Steiner, who has been recreating Terra Preta soils in Brazil since • Terra Preta soils contain 15-60 Mg/ha C in 0-0.3m but 1-3Mg/ha may be
1999. sufficient to enhance plant growth (GLASER et al.)
•Amount of applied organic matter (25% increase of Corg in • Surface oxidation increased cation exchange capacity (GLASER)
0-10 cm
• Increased the soil C content ~ 0.75% • Char decreased leaching significantly (LEHMANN)
•Applied Charcoal 11 t / ha • Char traps nutrients and supports microbial growth (Pietikainen)
•Mineral fertilizer: N (30), P (35), K (50), lime (2100 kg/ha) • Char increased available water capacity by more than 18% than
International Workshop on Anthropogenic Terra Preta Soils, surrounding soils (GLASER)
(July 2002 Brazil) • Char experiments have shown up to 266% more biomass growth
(STEINER) and 324% (Kishimoto and Sugiura)
8.5
for deposition 8 450 C
7.5 400 C
4. Good cation exchange 7
2
10
12
il
ita
Int
pH
Intra-particle volatile fatty acids deposits (Runkle et al.) occurring inside exothermic zone of pyrolysis are an
excellent microbial energy source (Westjohn et al.) for processing nitrogen compounds. We speculated that near the
dew point temperature a suitable material might require no outside fuel.
Leaching experiments were conducted of materials from different temperatures. Crushed and sieved (US #30
mesh), 20g samples was soaked for 5 minutes in 48% NH 4 NO 3 solution and allowed to dry for 24 hours. Samples
were leached with 100 ml rinses ( 8.0 pH). The 400C sample displayed very low leaching rates and was chosen as a
starting material.
4
Step
Step 3: 3: Process
Process MapMap
An additional benefit of the process is its ability
to combine with SOx and NOx from fossil fuel
exhaust. Both of the molecules are scrubbed
from the exhaust to form value added nutrients.
H2 Purifier/Dryer N2
Steam (27%)
(or alternate H2 System)
Steam Reformer
Compressor
Pyrolysis
Off-Gas Recycling Condenser
Water
Char Char Char Pump
Nutrient Mix/PK Clean
Ammonia Exhaust
Char
(Opt. Ammonia Purchased)
Metering Blending
Fluidized
Fossil Fuel Gases w/ CO 2/SO x/NOx Multistage Release
Cyclone ECOSS Fertilizer
5
Step 4:
Step 4: Bench
Bench
Scale Reactor
50 kg of char was prepared at 400C.
After initial heat up, no additional heat
was added and the pyrolysis unit ran
exothermically. The high temperature
rotary value discharged the char into a
closed container where it cooled. The
granular material was ground and
sieved to a uniform particle range. (20-
30 US Mesh)
Formation of ABC in
Fractures
6
The SEM to the left is of the sand like material
and was taken of the crushed interior. The
charred carbon framework of the plant cell Interior Image (Sand Like - 2000X)
structure is visible, appearing like plastic. The
volatile organics inside this char provide the
needed energy source for microbial action. The
ammonium bicarbonate appears as cotton-like
Charred
fibers.
Plant
The image below shows ammonium Framework
bicarbonate has filled the interior of the
large granular particles.
ABC Deposits
Bituminous
Diesel
Gasoline
Fuel
Propane
CO2 kg/MBTU
Liquified Petroleum Gases (LPG)
H2 & ECOSS
Current energy use ~400Ej/yr (Lysen) and CO2 is increasing by 6.1 Gt/yr
(IPCC). Each 1.0 MBTU H2/ECOSS represents 91kg (as measured, not
calculated) of sequestered CO2, then 6.1Gt/91kg equals 0.07Ej or 0.01.8% of
the current world consumption of energy.
7
Conclusions
Material Balance and Production Limits (Energy is not the limiting factor) At theoretical
maximum H2 –CO2 conversion there would only be enough CO2 to convert 61% of H2 to
ABC and since our target nitrogen content for the pyrogenic carbon is 10%, (requiring 45%
carbon by weight), our limit becomes the 20% carbon char (wt. 12) vs the 56% of ABC
(mol.wt. 79). The limit is therefore the carbon char as a carrier utilizing only 27% of avail-
able hydrogen but sequestering 91kg of carbon dioxide (as measured experimentally) per
million BTU of hydrogen utilized for energy. In addition, there is more than 91kg when the
carbon sequestered in the form of additional plant growth and CO2 equivalents from reduced
greenhouse gas emissions from lower power plant and fertilizer NOx release.
? Production of a nutrient inside carbon pores for physical slow release mechanism possi-
bly enhancing plant uptake and reducing fertilizer GHG emissions.
? Physical micro pore structure offers safe haven for enhanced microbial activity and in-
? Increased cation exchange and water holding capacity provide better plant-soil efficien-
cies.
? Provides a stable sequestration method where existing fertilizer business infrastructure
can profit
? Offers forestry and agriculture a method to enhance carbon sequestration and fiber/crop
yields
Danny Day
danny.day AT eprida.com Eprida
404-228-8687 6300 Powers Ferry Rd, Suite 307
http://www.eprida.com 8 Atlanta, GA 30339
The Potential for Biofertilisers
The growth in agricultural production during the last three decades has been accom-
panied by a sharp increase in the use of chemical fertilisers, causing serious concern
(Marothia, 1997). Foremost among these concerns is the effect of excessive fertiliser
(especially nitrogenous fertilisers) on the quality of soil and ground water.8
The promotion of biofertilisers is mainly carried out by the National Biofertiliser Devel-
opment Centre (Ghaziabad), which was set up in 1987. The main objectives of the
National Centre are to:
8 Water containing excess of nitrates can affect the blood’s ability to transport oxygen, with serious health implica-
tions (WHO, 1963).
The National Centre has the capacity to produce 375 tons of biofertilisers per year. In
addition to this, 58 commercial production units have been set up with government
support. India’s total production in 1998-99 was reported to be 16,000 tons.9 Rhizo-
bium accounts for the largest proportion (40%) of the total production in India. This
is followed by azatobacter. With the increase in the price of phosphate fertilisers, the
potential for the use of PSM has also increased.
Effectiveness of biofertilisers
A considerable amount of research has been done to establish the effectiveness of biofer-
tilisers on various crops, in different agro-climatic regions. Most agricultural universi-
ties, the ICAR and the National Biofertiliser Development Centre have carried out a
number of field trials to document the effectiveness of these micro-organisms. These
programmes show that the use of biofertilisers can have a significant effect on the yield
of most crops. However, their effectiveness is found to vary greatly, depending largely
on soil condition, temperature and farming practices. As an example, Table 3 shows the
effect of azatobacter on yield.
The potential of biofertilisers is evidenced by the fact that about 90% of Haryana’s soil
is deficient in nitrogen, indicating severe nutrient deficiency (Dahiya et al., 1993). The
dryland districts such as Bhiwani, Mohindergarh, Sirsa and Faridabad are particularly
low in nitrogen, and soils are short of organic matter due to poor vegetative cover, high
temperatures and the light texture of soil. Biofertilisers could play a role in providing
the much needed nutrients and improving soil conditions in these dryland areas, which
account for about 28% of the state’s total cultivable area.
Biofertilisers can also reduce the intensity of chemical fertiliser consumption, especially
in irrigated areas. With the increase in cropping intensity (see below), the use of chem-
ical fertilisers has increased significantly in these areas. The use of organic manure, on
the other hand, has not increased. As a result, many parts of Haryana face deteriorat-
ing soil conditions and increasing ground water contamination.
The suitability of biofertilisers for various crops grown in Haryana has been shown
through demonstrations conducted by the Hissar Centre of the National Biofertiliser
Development Centre (NBDC). Azatobacter and azospirillum, which can be used for a
wide range of crops, are estimated to have particularly large potential. For example,
NBDC experiments showed an increase in yield between 3 and 25% with the applica-
tion of azotobacter in cotton. Similarly, in the case of wheat, use of azotobacter resulted
in yield increases between 2 and 20%.10
10 National project on use and development of biofertilisers. Biofertiliser News, 1(2), December 1993.
Karnal District
In Karnal the main nutrient and pest problems relate to the district’s high cropping
intensity. Wheat-rice rotation has been common for some time now, and cropping inten-
sity has recently increased further with the introduction of short duration rice varieties
such as Govinda (90 days). Planting these varieties allows farmers to take two rice crops
between April and October. The first paddy crop is planted in April-May, as soon as
wheat has been harvested. This rice crop is ready for harvest by mid July. This is
followed immediately by the transplanting of fresh paddy seedlings. The second rice
crop is harvested by the end of October, to be followed by wheat, which is sown by
early November.
This very high intensity of cropping has worsened both the soil quality and pest problem
in parts of Karnal. It is extremely damaging to the soil condition, as large amounts of
nutrients are used continuously without replenishment. As a new crop is planted as
soon as the older crop is harvested (sometimes both activities are done simultaneously),
there is no time for proper land preparation and for using organic manure. As the use
of chemical fertilisers has increased to provide the required nutrients, soil and water
conditions have deteriorated.
The problem of pests and pesticide use in Karnal is largely confined to rice. Growing
two rice crops without a break is one factor. The continuation of rice plants in the same
field, and the high degree of moisture, enable pests to multiply without a break, leading
to particularly intense pest attacks in the second crop. Another reason is the popular-
ity of certain basmati varieties which are highly susceptible to pests and diseases. This
is particularly serious in one of the most popular of these varieties, called duplicate
basmati. This variety was introduced about five years ago from West UP, and became
very popular because of its high yields,12 and totally replaced the desi (traditional)
basmati variety in many areas. After performing well for three years, the variety began
to be affected by pests (stem borer, leaf folder and white back plant hopper) and diseases
(sheath blight, blast and bacterial leaf blight) two years ago. The attack was particu-
larly severe last year, forcing many farmers to stop planting basmati in general, and
duplicate basmati in particular. In one of the villages we studied, Kuuchhpura, farmers
made up to 15 pesticide applications last year but could not save the crop. This year,
very few farmers have planted basmati in the village.
11 The assimilation of atmospheric nitrogen by the roots of pulse (and other leguminous) crops is carried out
by the nodules formed in the roots of these plants. The low degree of nodulation suggests that their ability to
assimilate atmospheric nitrogen is low and that they could benefit from the use of rhizobium.
12 Compared to the average yield of 10 quintal/acre from desi basmati, the yields of duplicate basmati were
about 20 quintal/acre.
The District Agriculture Department is responsible for the sale of rhizobium in Bhiwani.
Being a major gram growing district, it was allocated the largest amount of rhizobium
last year and its sale to farmers is subsidised at the rate of 50%.
The main pest problem in Bhiwani concerns cotton, which is attacked by American,
pink and spotted bollworm, white fly and jassid. These pests have become resistant to
most pesticides. According to a study of pesticide use in Bhiwani in 1998, about 70%
of farmers reported that they were unable to control pests with pesticides (Saini and
Jaglan, 1998). Some of these farmers had used up to 11 pesticide applications.
The pest problem in Bhiwani is closely linked with the spread of irrigation facilities.
Large parts of Bhiwani district are irrigated by the Indira Gandhi Canal, which suffers
from large scale seepage. This has led to a rise in the groundwater level from 50-60 feet
below the surface in the past to 5-10 feet at present in many areas. As a result, water
logging and high humidity are serious problems in many areas of the district. Apart
from causing direct damage, this has also created favourable conditions for the growth
of pests. Consequently, the problem of pests has become extremely serious in the district
during the last five years.
The pest problem caused the area under cotton to decline in the second half of the
1990s from 57, 000 hectares in 1996-97 to 51,000 hectares in 1999-2000.14 As in rice
We observed a shift back in favour of desi cotton in one of the divisions of Bhiwani
following severe losses to pests to the American varieties. Whilst many more farmers
would prefer to shift to desi cotton varieties, as they provide stable yields, their whole-
sale prices are too low. In addition it appears that the state agriculture department
prefers to promote long staple American varieties, as they have large domestic and
export markets.
Farmers’ Perspectives
We selected 11 villages from the two districts, six villages from Karnal and five from
Bhiwani, in which to interview farmers to establish their awareness and use of biofer-
tilisers and biopesticides. A total of 74 farmers from these villages were interviewed, and
were mainly selected because they had attended one of the demonstration programmes
carried out by government agencies to promote IPM, biopesticides and biofertilisers
(58 of the farmers, or about 80% of the sample). However, some farmers who had not
been to the programmes were also interviewed (16 farmers). All the farmers were men;
only men had participated in the demonstration programmes, and we were told that
men take the decisions about the types of fertilisers and pesticides to be used.
The farmers included in the study represent the range of small, medium and large
farmers. While 29% of the farmers have less than 5 acres of land, 46% have between
5 and 20 acres. 25% of the farmers have landholdings larger than 20 acres. In terms
of education, about one third of the farmers have studied up to class 10 or more. A
semi-structured questionnaire was used for interviews, which were conducted in
farmers’ homes.
Findings: Biopesticides
Although biopesticides and bio-control agents are important components of IPM, the
IPM programmes being conducted by various agencies put very little emphasis on these
agents. None of the farmers we interviewed had ever used biopesticides, and few were
even aware they existed. We found that none of the farmers had even used neem, widely
believed to be commonly used by Indian farmers.
In fact, we found that IPM itself was not being practised by most farmers. While some
of the farmers were aware of IPM practices, such as the need for monitoring and
2. Lack of skills. Almost all the farmers, including all of those who were aware of IPM,
reported that they lacked the skills necessary to practise IPM. Their ability to practise
IPM was, for example, severely constrained by the fact that most of them could not differ-
entiate between harmful and beneficial insects. In fact, many farmers thought that all
insects were a potential threat to their crop and had to be destroyed. They were also not
able to work out economic thresholds15 to determine the timings of pesticide application.
3. Lack of faith in IPM. This factor was found to be very important amongst 60% of
farmers in Karnal. Although almost all of them were aware of IPM, they felt that they
did not have sufficient faith in it to reduce the use of chemical pesticides. Many of
them felt that the support from the agricultural department was not adequate for them
to try IPM practices, which were considered risky. As the CIPM personnel do not keep
in touch with the farmers after IPM demonstrations, they felt that they would not get
adequate advice and support if things went wrong. Similarly, the local extension
workers (ADOs) are not sufficiently trained in IPM to instil confidence in the farmers.
The issue of skills and confidence is obviously linked to the intensity of training
provided by the IPM agencies to farmers and extension workers. We found that the
training is very basic and superficial, being conducted for three to four days in a
village, during which 30 villagers and five extension workers are trained. The farmers
felt that the training was not intensive and did not impart sufficient skills for them
to feel competent and confident in following IPM practices.
15 The economic threshold is the level of pest population at which the damage to crop justifies the use of pest
control methods.
The role of shopkeepers and dealers is particularly important because many farmers
(58%) purchase their pesticides on credit. This gives the shopkeepers strong control
over the amount and choice of pesticides used. It also makes it easier for the shop-
keepers to sell spurious pesticides.
Finally, we found that the knowledge of the State Agricultural Department about
biopesticides was extremely limited. This was particularly true of the village level
workers (ADOs), but also the case even in the Central IPM office in Faridabad. Consid-
ering the importance given to the use of biopesticides by national government agen-
cies, the neglect of biopesticides at the state and district level is difficult to understand.
The main emphasis is on the monitoring of pest populations and the use of economic
thresholds, which farmers find too difficult and time consuming. Further, the Haryana
Findings: Biofertilisers
Few (19%) farmers have ever used biofertilisers in the two districts. Their number was
especially small in Karnal, where only three out of 40 farmers had used them. In
Bhiwani about 75% of farmers were not even aware of biofertilisers; the proportion of
such farmers was even higher in Karnal (85%).
The most important reason for this lack of awareness is the fact that agriculture exten-
sion workers do not promote biofertilisers. On the whole, only 15% of farmers had
been told about biofertilisers by the extension workers. The emphasis on biofertilisers
was particularly low in Karnal, where only one farmer out of 40 had heard about them
from extension workers.
The District Agricultural Departments do not have a positive attitude towards biofer-
tilisers. They feel that their quality is poor, and their performance totally unreliable.
Therefore, they are not prepared to risk their reputation and good will with the farmers
by recommending them. The extension services run by the Haryana Agriculture Univer-
sity (krishi vigyan kendra) feel that in areas of wheat/paddy rotation, such as Karnal,
the potential of biofertilisers is low. The farmers in these areas can get the same yield
by using the recommended dose of chemical fertilisers. As these fertilisers are easy to
use, the farmers prefer them. Biofertilisers have to be stored and applied in conditions
which are suitable for the multipication of micro-organisms. This requires special facil-
ities and care, which farmers are often unable to provide. Chemical fertilisers, on the
other hand, can be stored and applied without special care. In fact, the KVK in Karnal
does not recommend the use of biofertilisers at all.
Nevertheless, the extension workers in Bhiwani are required to sell a fixed number of
rhizobium packets. This explains the larger number of farmers who are aware of biofer-
tilisers, and have used them in this district. But we found that a large proportion of the
rhizobium allotted to the district is not sold to the farmers, and is allowed to go to
waste. The ADOs say that the quality and performance is so poor that the farmers are
not interested in buying it. The quota is shown as sold in official records, and the
payment is made by the ADOs from their salary.16 The fact that the rhizobium meant
for sale in various pulse growing districts is not being used by farmers is widely known
to both the State Agricultural Department and the National Biofertiliser Development
16 For example, one of the ADOs in Bhiwani was given a quota of 2000 packets of rhizobium this year. He
could manage to sell only about 200 packets, mostly to his contact farmers. But these have not actually been
used by the farmers. He feels that the contact farmers accept biofertilisers because they want to stay in the good
books of the ADOs, from whom they receive subsidised or free goods, such as seed kits. He will have to pay
to the Agricultural Department Rs. 8,000/- (@Rs. 4.00 a packet).
Out of 19 farmers who were aware of biofertilisers, 14 had used them, showing that
farmers are prepared to try biofertilisers. However, most of these farmers stopped using
them after one crop - only three were still using them. Two reasons were reported to
be important for the discontinuation of use: lack of availability and poor performance.
Availability
Many farmers who stopped using biofertilisers reported that this was partly because the
supply was extremely unreliable. This was largely because biofertilisers were not being
sold by most shops. While none of the shops stock biofertilisers in Karnal, two shops
in Bhiwani do. The shopkeepers, in turn, say that they do not stock biofertilisers
because sales are poor. One of the Bhiwani shops, for example, has been stocking biofer-
tilisers from National Fertilisers Ltd. for the last four years but has sold only 30 packets.
Q uality
It is clear that the poor quality and performance of biofertilisers present serious prob-
lems. Most studies suggest that the biofertilisers being sold in the market are contam-
inated and have a low count of micro-organisms. It is therefore not surprising that their
performance is poor and uneven. For example, in a survey of rhizobium carried out by
ICRISAT, 90% of samples from India were found to have a rhizobia count lower than
that required for effective performance (Singleton et al., 1996). Incidentally, this
problem exists in most developing countries. For example, in a survey of 12 develop-
ing countries, only 19% of the samples met the standards prevalent in developed coun-
tries (Singleton et al., 1996).
As agro-climatic conditions and soil characteristics vary widely, a large range of strains
of each biofertiliser needs to be isolated for each area. The problem of identifying suit-
able strains is particularly serious in north India, as many of the strains do not survive
the very hot temperatures prevalent in these areas. Until strains which can tolerate wide
variations in temperature can be identified, the performance of biofertilisers will remain
uneven. The Haryana Agriculture University is reported to be working in this direction
and has developed improved strains for pearl millet, wheat, mustard, potatoes, and
flowering plants. These are, however, yet to be used in large scale production.
The production technology employed in India is inefficient and is responsible for most
of the contamination common in Indian biofertilisers. Generally, production is under-
taken by the flask method, which is unsuitable for large scale production. Although
some firms use fermenters, they lack the sophisticated controls and monitoring facili-
ties necessary to regulate factors such as pH, temperature and aeration. As a result the
quality of the bacterial broth is often poor and uneven.
Another problem relates to the fact that Indian producers do not sterilise the carriers
used for mixing the bacterial solution. For example, both the producers in Haryana, the
Hissar Biofertiliser Centre and the HAU, use non-sterilised charcoal, as they do not
have facilities to sterilise large amounts of charcoal in a short time. This is an impor-
tant cause of the poor quality and short shelf life of these biofertilisers (Singh et al.,
1999). Although India has ISI (Indian Standards Institution) standards for some of the
biopesticides (rhizobium and azatobacter), they are not enforced. This is reportedly
because the ISI lacks facilities to test biofertilisers.
Conclusions
Biopesticides
The problem of pests, the development of pesticide resistance and the excessive use of
pesticides need to be seen in the totality of the agricultural system. Our study shows that
in Karnal and Bhiwani the problem is linked to the increase in cropping intensity (three
crops in Karnal), the expansion of irrigation facilities (Bhiwani), the release and adop-
tion of susceptible varieties (govinda and basmati rice in Karnal, and American cotton
varieties in Bhiwani), purchase of pesticides on credit (in both the districts) and inap-
propriate agricultural practices (the use of contract labour for pesticide application,
using power spraying machines in Karnal). In the circumstances, mere reliance on pest
control, without correcting the basic problem in the system, will not produce sustain-
able results.
18
18 G ATEKEEPER SERIES N O .SA91
.SA93
Gatekeeper Series no. 93
A Study of
Biopesticides and
Biofertilisers in
Haryana, India
Ghayur Alam
2000
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2000
The study found that for the use of biopesticides, a key problem was that
departments promoting Integrated Pest Management (IPM) have very little
knowledge and experience of biopesticides, and most state agricultural universi-
ties, on whose recommendations pest control methods are promoted, do not
tend to recommend biopesticides. In the absence of active promotion by the
agriculture department, the demand for these products has not developed, and
most private shops and dealers do not stock and sell biopesticides. The paper
recommends that the agricultural departments and universities pay greater
attention to the promotion of biopesticides, that IPM training is improved, and
that there is a greater focus on cropping techniques and varieties which do not
require such a dependence on pesticides.
In the case of biofertilisers, their poor quality and performance is a major factor
in their limited uptake by farmers. This is primarily linked to inappropriate
strains and inefficient production technology. As a result it is recommended that
research and development to identify more suitable strains, to develop better
production technology and quality control methods is greatly increased, and
that in the meantime the various grants and subsidies on biofertilisers are divert-
ed to support these R&D programmes.
Introduction
The use of chemical pesticides and fertilisers in Indian agriculture has seen a sharp
increase in recent years. In some areas, such as Haryana, Punjab and west Uttar
Pradesh, it has reached alarming levels. The heavy use of these chemicals has already
caused grave damage to health, ecosystems and ground water. It is therefore increasingly
urgent that environmentally friendly methods of improving soil fertility and pests and
disease control are used.
Cotton 44.5
Paddy 22.8
Jowar 8.9
Fruits and Vegetables 7.0
Wheat 6.4
Arhar 2.8
Other 7.6
Total 100.00
Source: Dudani and Sengupta, 1991
The intensive use of pesticides in agriculture is a cause of serious concern. The problem
is especially serious because of the development of resistance to pesticides in important
pests and the presence of pesticide residue in agricultural and dairy products.
Pesticide resistance in agriculture was first noticed in India in 1963 when a number of
serious pests were reported to have become resistant to DDT and HCH (two of the
most commonly used pesticides during the 1960s and 1970s). Since then the number
of pests with pesticide resistance has increased. The most serious problem of resistance
is witnessed in cotton, for which American bollworm is a serious pest. The bollworm
has developed resistance to almost all pesticides in a number of regions, and is partic-
ularly serious in parts of Punjab, Haryana, Andhra Pradesh, Karnataka and Maha-
rashtra. Other important pests of cotton, white fly and jassid, have also developed
pesticide resistance in some places.
Growing pesticide resistance has meant that a large proportion of agricultural produc-
tion is lost to pests. According to some estimates, these losses amount to between 20-
30% of total production (Mehrotra, 1989). The losses are particularly serious in cotton.
For example, cotton production in Punjab declined by about 50% during 1997 and
1998,1 causing a number of cotton farmers to commit suicide in the affected areas.2
Pesticide resistance has mainly been caused by excessive and indiscriminate use of pesti-
cides (Jayaraj, 1989). Pesticides of spurious quality, which are commonly sold in small
towns and villages, have also contributed to resistance in many areas. For example, in
Bidar (Karnataka) where the problem of pest resistance has become extremely serious,
more than 50 brands of pesticides were found to be sub-standard in 1998-99. In another
incident, the licenses of 115 pesticide producers were cancelled in Punjab for selling
1 “Another bad season for cotton farmers”, Hindustan Times, September 17, 1998.
2 For example, in Punjab 133 farmers were reported to have committed suicide in 1998 due to crop failure
caused by pest attack. “Another farmer in debt trap commits suicide”, Hindustan Times, October 4, 1998.
The other important problem caused by the excessive and inappropriate use of chem-
ical pesticides concerns the presence of pesticide residue in food. Many of the pesti-
cides currently being used have a tendency to survive in plants for a long time. They also
enter the food chain and are found in meat and dairy products. The problem of pesti-
cide residue is already a serious threat to health and environment in India. The inci-
dence of pesticide residue is much higher in India than in developed countries. For
example, according to one study, more than 80% of milk samples tested in India were
found to contain residues of DDT and HCH (Handa, undated). According to another
study, residue of DDT and benzene hexachloride, both suspected carcinogens, were
found in breast milk samples collected from mothers in Punjab. The amount of residue
was very high and babies were ingesting 21 times the amount of these chemicals consid-
ered acceptable through their mothers’ milk (Jumanah, 1994).
Compared to this, only 0.17% of samples tested in the US in 1990 were found to
contain residues over the acceptable limits.4 Similarly, in a study in the UK, only 1% of
the samples were found to contain residues above the prescribed limit.5
It is clear that the excessive use of chemical pesticides in agriculture is a serious cause
of concern. It is, therefore, important that alternative, environmentally friendly methods
of plant protection are adopted, such as integrated pest management (IPM) techniques,
including the use of biopesticides.
The most commonly used biopesticides include Bacillus thuringiensis (Bt), Baculoviruses
and neem. In addition to these, trichoderma, which is a fungicide, is also used. Bio-
control agents, such as Trichogramma, are parasites and predators of pests and their
3 “Another bad season for cotton farmers”, Hindustan Times, September 17, 1998.
4 “Current Pesticide Residue Levels in Food are Safe”, Pesticide Outlook (5)1, Feb 94. Cambridge.
5 “Latest UK Pesticide Residue Results Published”, Pesticide Outlook, Dec 1994, pp8. Cambridge.
• Bacillus thuringiensis (Bt). Bacillus thuringiensis is the most commonly used biopes-
ticide globally. It is primarily a pathogen of lepidopterous pests which are some of
the most damaging. These include American bollworm in cotton and stem borers in
rice. When ingested by pest larvae, Bt releases toxins which damage the mid gut of
the pest, eventually killing it. Bt based pesticides are being marketed by three compa-
nies in India. The total sale in 1999 was about 70 tons.6
• Baculoviruses. These are target specific viruses which can infect and destroy a number
of important plant pests. They are particularly effective against the lepidopterous
pests of cotton, rice and vegetables. Their large-scale production poses certain diffi-
culties, so their use has been limited to small areas. They are not available commer-
cially in India, but are being produced on a small scale by various IPM centres and
state agricultural departments.
• Neem. Derived from the neem tree (Azadirachta indica), this contains several chem-
icals, including ‘azadirachtin’, which affects the reproductive and digestive process
of a number of important pests. Recent research carried out in India and abroad has
led to the development of effective formulations of neem, which are being commer-
cially produced. As neem is non-toxic to birds and mammals and is non-carcinogenic,
its demand is likely to increase. However, the present demand is very small. Although
more than 100 firms are registered to produce neem-based pesticides in India, only a
handful are actually producing it. Furthermore, very little of the production is sold
locally, most being for export markets.
Whilst India does not have technology to produce Trichogramma on a large scale, they
are being produced in small scale facilities for local use, mostly by sugar mills and coop-
eratives, state agricultural departments, IPM centres and agricultural universities.
Recently, some companies have started marketing Trichogramma through direct selling.
But the volume of sale is very small. Trichogramma eggs have to be used within a short
period (before the eggs hatch). This limits their production and marketing on a large
scale, and is also the reason why Trichogramma is not sold through dealers and shop-
keepers.
7 “Integrated Pest Management Module for Dryland Regions - ICAR Trials in Cotton Fields Successful”.
Hindu Business Line, 4.1.1999.
The promotion of biofertilisers is mainly carried out by the National Biofertiliser Devel-
opment Centre (Ghaziabad), which was set up in 1987. The main objectives of the
National Centre are to:
8 Water containing excess of nitrates can affect the blood’s ability to transport oxygen, with serious health implica-
tions (WHO, 1963).
The National Centre has the capacity to produce 375 tons of biofertilisers per year. In
addition to this, 58 commercial production units have been set up with government
support. India’s total production in 1998-99 was reported to be 16,000 tons.9 Rhizo-
bium accounts for the largest proportion (40%) of the total production in India. This
is followed by azatobacter. With the increase in the price of phosphate fertilisers, the
potential for the use of PSM has also increased.
Effectiveness of biofertilisers
A considerable amount of research has been done to establish the effectiveness of biofer-
tilisers on various crops, in different agro-climatic regions. Most agricultural universi-
ties, the ICAR and the National Biofertiliser Development Centre have carried out a
number of field trials to document the effectiveness of these micro-organisms. These
programmes show that the use of biofertilisers can have a significant effect on the yield
of most crops. However, their effectiveness is found to vary greatly, depending largely
on soil condition, temperature and farming practices. As an example, Table 3 shows the
effect of azatobacter on yield.
The potential of biofertilisers is evidenced by the fact that about 90% of Haryana’s soil
is deficient in nitrogen, indicating severe nutrient deficiency (Dahiya et al., 1993). The
dryland districts such as Bhiwani, Mohindergarh, Sirsa and Faridabad are particularly
low in nitrogen, and soils are short of organic matter due to poor vegetative cover, high
temperatures and the light texture of soil. Biofertilisers could play a role in providing
the much needed nutrients and improving soil conditions in these dryland areas, which
account for about 28% of the state’s total cultivable area.
Biofertilisers can also reduce the intensity of chemical fertiliser consumption, especially
in irrigated areas. With the increase in cropping intensity (see below), the use of chem-
ical fertilisers has increased significantly in these areas. The use of organic manure, on
the other hand, has not increased. As a result, many parts of Haryana face deteriorat-
ing soil conditions and increasing ground water contamination.
The suitability of biofertilisers for various crops grown in Haryana has been shown
through demonstrations conducted by the Hissar Centre of the National Biofertiliser
Development Centre (NBDC). Azatobacter and azospirillum, which can be used for a
wide range of crops, are estimated to have particularly large potential. For example,
NBDC experiments showed an increase in yield between 3 and 25% with the applica-
tion of azotobacter in cotton. Similarly, in the case of wheat, use of azotobacter resulted
in yield increases between 2 and 20%.10
10 National project on use and development of biofertilisers. Biofertiliser News, 1(2), December 1993.
Karnal District
In Karnal the main nutrient and pest problems relate to the district’s high cropping
intensity. Wheat-rice rotation has been common for some time now, and cropping inten-
sity has recently increased further with the introduction of short duration rice varieties
such as Govinda (90 days). Planting these varieties allows farmers to take two rice crops
between April and October. The first paddy crop is planted in April-May, as soon as
wheat has been harvested. This rice crop is ready for harvest by mid July. This is
followed immediately by the transplanting of fresh paddy seedlings. The second rice
crop is harvested by the end of October, to be followed by wheat, which is sown by
early November.
This very high intensity of cropping has worsened both the soil quality and pest problem
in parts of Karnal. It is extremely damaging to the soil condition, as large amounts of
nutrients are used continuously without replenishment. As a new crop is planted as
soon as the older crop is harvested (sometimes both activities are done simultaneously),
there is no time for proper land preparation and for using organic manure. As the use
of chemical fertilisers has increased to provide the required nutrients, soil and water
conditions have deteriorated.
The problem of pests and pesticide use in Karnal is largely confined to rice. Growing
two rice crops without a break is one factor. The continuation of rice plants in the same
field, and the high degree of moisture, enable pests to multiply without a break, leading
to particularly intense pest attacks in the second crop. Another reason is the popular-
ity of certain basmati varieties which are highly susceptible to pests and diseases. This
is particularly serious in one of the most popular of these varieties, called duplicate
basmati. This variety was introduced about five years ago from West UP, and became
very popular because of its high yields,12 and totally replaced the desi (traditional)
basmati variety in many areas. After performing well for three years, the variety began
to be affected by pests (stem borer, leaf folder and white back plant hopper) and diseases
(sheath blight, blast and bacterial leaf blight) two years ago. The attack was particu-
larly severe last year, forcing many farmers to stop planting basmati in general, and
duplicate basmati in particular. In one of the villages we studied, Kuuchhpura, farmers
made up to 15 pesticide applications last year but could not save the crop. This year,
very few farmers have planted basmati in the village.
11 The assimilation of atmospheric nitrogen by the roots of pulse (and other leguminous) crops is carried out
by the nodules formed in the roots of these plants. The low degree of nodulation suggests that their ability to
assimilate atmospheric nitrogen is low and that they could benefit from the use of rhizobium.
12 Compared to the average yield of 10 quintal/acre from desi basmati, the yields of duplicate basmati were
about 20 quintal/acre.
Bhiwani District
In Bhiwani, the focus of the study is on cotton and gram, which, along with wheat and
mustard are the main crops in the area. The use of chemical fertilisers is comparatively
low in Bhiwani, being used only on wheat and cotton, and not at all on gram and
mustard. But, as in Karnal, use of organic manure is not common and the condition of
the soil is poor. Three biofertilisers have potential for Bhiwani: rhizobium for gram and
azatobacter and PSM for wheat. The potential of rhizobium is reported to be particu-
larly high in Bhiwani because the level of nodulation is very low.
The District Agriculture Department is responsible for the sale of rhizobium in Bhiwani.
Being a major gram growing district, it was allocated the largest amount of rhizobium
last year and its sale to farmers is subsidised at the rate of 50%.
The main pest problem in Bhiwani concerns cotton, which is attacked by American,
pink and spotted bollworm, white fly and jassid. These pests have become resistant to
most pesticides. According to a study of pesticide use in Bhiwani in 1998, about 70%
of farmers reported that they were unable to control pests with pesticides (Saini and
Jaglan, 1998). Some of these farmers had used up to 11 pesticide applications.
The pest problem in Bhiwani is closely linked with the spread of irrigation facilities.
Large parts of Bhiwani district are irrigated by the Indira Gandhi Canal, which suffers
from large scale seepage. This has led to a rise in the groundwater level from 50-60 feet
below the surface in the past to 5-10 feet at present in many areas. As a result, water
logging and high humidity are serious problems in many areas of the district. Apart
from causing direct damage, this has also created favourable conditions for the growth
of pests. Consequently, the problem of pests has become extremely serious in the district
during the last five years.
The pest problem caused the area under cotton to decline in the second half of the
1990s from 57, 000 hectares in 1996-97 to 51,000 hectares in 1999-2000.14 As in rice
We observed a shift back in favour of desi cotton in one of the divisions of Bhiwani
following severe losses to pests to the American varieties. Whilst many more farmers
would prefer to shift to desi cotton varieties, as they provide stable yields, their whole-
sale prices are too low. In addition it appears that the state agriculture department
prefers to promote long staple American varieties, as they have large domestic and
export markets.
Farmers’ Perspectives
We selected 11 villages from the two districts, six villages from Karnal and five from
Bhiwani, in which to interview farmers to establish their awareness and use of biofer-
tilisers and biopesticides. A total of 74 farmers from these villages were interviewed, and
were mainly selected because they had attended one of the demonstration programmes
carried out by government agencies to promote IPM, biopesticides and biofertilisers
(58 of the farmers, or about 80% of the sample). However, some farmers who had not
been to the programmes were also interviewed (16 farmers). All the farmers were men;
only men had participated in the demonstration programmes, and we were told that
men take the decisions about the types of fertilisers and pesticides to be used.
The farmers included in the study represent the range of small, medium and large
farmers. While 29% of the farmers have less than 5 acres of land, 46% have between
5 and 20 acres. 25% of the farmers have landholdings larger than 20 acres. In terms
of education, about one third of the farmers have studied up to class 10 or more. A
semi-structured questionnaire was used for interviews, which were conducted in
farmers’ homes.
Findings: Biopesticides
Although biopesticides and bio-control agents are important components of IPM, the
IPM programmes being conducted by various agencies put very little emphasis on these
agents. None of the farmers we interviewed had ever used biopesticides, and few were
even aware they existed. We found that none of the farmers had even used neem, widely
believed to be commonly used by Indian farmers.
In fact, we found that IPM itself was not being practised by most farmers. While some
of the farmers were aware of IPM practices, such as the need for monitoring and
2. Lack of skills. Almost all the farmers, including all of those who were aware of IPM,
reported that they lacked the skills necessary to practise IPM. Their ability to practise
IPM was, for example, severely constrained by the fact that most of them could not differ-
entiate between harmful and beneficial insects. In fact, many farmers thought that all
insects were a potential threat to their crop and had to be destroyed. They were also not
able to work out economic thresholds15 to determine the timings of pesticide application.
3. Lack of faith in IPM. This factor was found to be very important amongst 60% of
farmers in Karnal. Although almost all of them were aware of IPM, they felt that they
did not have sufficient faith in it to reduce the use of chemical pesticides. Many of
them felt that the support from the agricultural department was not adequate for them
to try IPM practices, which were considered risky. As the CIPM personnel do not keep
in touch with the farmers after IPM demonstrations, they felt that they would not get
adequate advice and support if things went wrong. Similarly, the local extension
workers (ADOs) are not sufficiently trained in IPM to instil confidence in the farmers.
The issue of skills and confidence is obviously linked to the intensity of training
provided by the IPM agencies to farmers and extension workers. We found that the
training is very basic and superficial, being conducted for three to four days in a
village, during which 30 villagers and five extension workers are trained. The farmers
felt that the training was not intensive and did not impart sufficient skills for them
to feel competent and confident in following IPM practices.
15 The economic threshold is the level of pest population at which the damage to crop justifies the use of pest
control methods.
The role of shopkeepers and dealers is particularly important because many farmers
(58%) purchase their pesticides on credit. This gives the shopkeepers strong control
over the amount and choice of pesticides used. It also makes it easier for the shop-
keepers to sell spurious pesticides.
Finally, we found that the knowledge of the State Agricultural Department about
biopesticides was extremely limited. This was particularly true of the village level
workers (ADOs), but also the case even in the Central IPM office in Faridabad. Consid-
ering the importance given to the use of biopesticides by national government agen-
cies, the neglect of biopesticides at the state and district level is difficult to understand.
The main emphasis is on the monitoring of pest populations and the use of economic
thresholds, which farmers find too difficult and time consuming. Further, the Haryana
Findings: Biofertilisers
Few (19%) farmers have ever used biofertilisers in the two districts. Their number was
especially small in Karnal, where only three out of 40 farmers had used them. In
Bhiwani about 75% of farmers were not even aware of biofertilisers; the proportion of
such farmers was even higher in Karnal (85%).
The most important reason for this lack of awareness is the fact that agriculture exten-
sion workers do not promote biofertilisers. On the whole, only 15% of farmers had
been told about biofertilisers by the extension workers. The emphasis on biofertilisers
was particularly low in Karnal, where only one farmer out of 40 had heard about them
from extension workers.
The District Agricultural Departments do not have a positive attitude towards biofer-
tilisers. They feel that their quality is poor, and their performance totally unreliable.
Therefore, they are not prepared to risk their reputation and good will with the farmers
by recommending them. The extension services run by the Haryana Agriculture Univer-
sity (krishi vigyan kendra) feel that in areas of wheat/paddy rotation, such as Karnal,
the potential of biofertilisers is low. The farmers in these areas can get the same yield
by using the recommended dose of chemical fertilisers. As these fertilisers are easy to
use, the farmers prefer them. Biofertilisers have to be stored and applied in conditions
which are suitable for the multipication of micro-organisms. This requires special facil-
ities and care, which farmers are often unable to provide. Chemical fertilisers, on the
other hand, can be stored and applied without special care. In fact, the KVK in Karnal
does not recommend the use of biofertilisers at all.
Nevertheless, the extension workers in Bhiwani are required to sell a fixed number of
rhizobium packets. This explains the larger number of farmers who are aware of biofer-
tilisers, and have used them in this district. But we found that a large proportion of the
rhizobium allotted to the district is not sold to the farmers, and is allowed to go to
waste. The ADOs say that the quality and performance is so poor that the farmers are
not interested in buying it. The quota is shown as sold in official records, and the
payment is made by the ADOs from their salary.16 The fact that the rhizobium meant
for sale in various pulse growing districts is not being used by farmers is widely known
to both the State Agricultural Department and the National Biofertiliser Development
16 For example, one of the ADOs in Bhiwani was given a quota of 2000 packets of rhizobium this year. He
could manage to sell only about 200 packets, mostly to his contact farmers. But these have not actually been
used by the farmers. He feels that the contact farmers accept biofertilisers because they want to stay in the good
books of the ADOs, from whom they receive subsidised or free goods, such as seed kits. He will have to pay
to the Agricultural Department Rs. 8,000/- (@Rs. 4.00 a packet).
Out of 19 farmers who were aware of biofertilisers, 14 had used them, showing that
farmers are prepared to try biofertilisers. However, most of these farmers stopped using
them after one crop - only three were still using them. Two reasons were reported to
be important for the discontinuation of use: lack of availability and poor performance.
Availability
Many farmers who stopped using biofertilisers reported that this was partly because the
supply was extremely unreliable. This was largely because biofertilisers were not being
sold by most shops. While none of the shops stock biofertilisers in Karnal, two shops
in Bhiwani do. The shopkeepers, in turn, say that they do not stock biofertilisers
because sales are poor. One of the Bhiwani shops, for example, has been stocking biofer-
tilisers from National Fertilisers Ltd. for the last four years but has sold only 30 packets.
Quality
It is clear that the poor quality and performance of biofertilisers present serious prob-
lems. Most studies suggest that the biofertilisers being sold in the market are contam-
inated and have a low count of micro-organisms. It is therefore not surprising that their
performance is poor and uneven. For example, in a survey of rhizobium carried out by
ICRISAT, 90% of samples from India were found to have a rhizobia count lower than
that required for effective performance (Singleton et al., 1996). Incidentally, this
problem exists in most developing countries. For example, in a survey of 12 develop-
ing countries, only 19% of the samples met the standards prevalent in developed coun-
tries (Singleton et al., 1996).
As agro-climatic conditions and soil characteristics vary widely, a large range of strains
of each biofertiliser needs to be isolated for each area. The problem of identifying suit-
able strains is particularly serious in north India, as many of the strains do not survive
the very hot temperatures prevalent in these areas. Until strains which can tolerate wide
variations in temperature can be identified, the performance of biofertilisers will remain
uneven. The Haryana Agriculture University is reported to be working in this direction
and has developed improved strains for pearl millet, wheat, mustard, potatoes, and
flowering plants. These are, however, yet to be used in large scale production.
The production technology employed in India is inefficient and is responsible for most
of the contamination common in Indian biofertilisers. Generally, production is under-
taken by the flask method, which is unsuitable for large scale production. Although
some firms use fermenters, they lack the sophisticated controls and monitoring facili-
ties necessary to regulate factors such as pH, temperature and aeration. As a result the
quality of the bacterial broth is often poor and uneven.
Another problem relates to the fact that Indian producers do not sterilise the carriers
used for mixing the bacterial solution. For example, both the producers in Haryana, the
Hissar Biofertiliser Centre and the HAU, use non-sterilised charcoal, as they do not
have facilities to sterilise large amounts of charcoal in a short time. This is an impor-
tant cause of the poor quality and short shelf life of these biofertilisers (Singh et al.,
1999). Although India has ISI (Indian Standards Institution) standards for some of the
biopesticides (rhizobium and azatobacter), they are not enforced. This is reportedly
because the ISI lacks facilities to test biofertilisers.
Conclusions
Biopesticides
The problem of pests, the development of pesticide resistance and the excessive use of
pesticides need to be seen in the totality of the agricultural system. Our study shows that
in Karnal and Bhiwani the problem is linked to the increase in cropping intensity (three
crops in Karnal), the expansion of irrigation facilities (Bhiwani), the release and adop-
tion of susceptible varieties (govinda and basmati rice in Karnal, and American cotton
varieties in Bhiwani), purchase of pesticides on credit (in both the districts) and inap-
propriate agricultural practices (the use of contract labour for pesticide application,
using power spraying machines in Karnal). In the circumstances, mere reliance on pest
control, without correcting the basic problem in the system, will not produce sustain-
able results.
18
18 GATEKEEPER SERIES NO.SA91
NO.SA93
The following policy measures need to be taken urgently in order to reduce excessive
use of chemical pesticides.
• Focus on sustainable agriculture by promoting: a) disease and pest resistant, and espe-
cially traditional, varieties; b) judicious inter-cropping and c) reduced crop intensity.
• Improvement in the intensity of training for IPM. The focus should be on the quality
of training and not on the number of farmers trained. The training should be followed
by regular contact with the trained farmers for providing continous support.
• Promotion of the use of biopesticides by the state agricultural departments and IPM
workers. The state agricultural universities, which have decisive influence over what
pest control methods are promoted by governmental agencies, should pay greater
attention to biopesticides.
Biofertilisers
Despite the Indian government’s efforts to promote the production and use of biofer-
tilisers, our study found that biofertilisers have found little acceptance among farmers
in Haryana. The problems of unavailability of biofertilisers and their poor quality are
linked. On the one hand, we find that both the State Agriculture Department and shop-
keepers are unwilling to stock and sell biofertilisers as they feel that their quality is
unreliable. On the other hand, the low demand for biofertilisers has prevented large
investment in advanced production and storage facilities, which are required for
improving the quality. It is, therefore, clear that the two problems have to be seen in
their totality, and a new policy is needed, some elements of which are as follows:
• The present policy of providing grants and low interest loans to biofertiliser produc-
ers should be abolished; this has resulted in the setting up of a large number of inef-
ficient plants, which cannot produce good quality biofertilisers.
• The policy of marketing biofertilisers at very low prices should also be stopped. These
prices are too low to attract adequate investment in modern manufacturing facilities.
Take the example of rhizobium. A 200 gram packet of biofertiliser, which is supposed
to replace about 30 kilograms of urea (a commonly used chemical fertiliser), is
purchased by the Agricultural Department for Rs. 8/ packet. This price is not enough
to justify investment in facilities such as charcoal sterilisation plants and cold chain
for storage and transportation. Rhizobium is sold to farmers at a subsidised rate of
Rs. 4/-. Our discussions with farmers suggest they feel that nothing so cheap can
provide much nutrition to the plants, and do not value it. The price of biofertilisers
should have some relationship with the price of the chemical fertiliser it replaces.
Only then will the producers, the shopkeepers and the farmers begin to take biofer-
tilisers seriously.
• The storage and application of biofertilisers require special facilities and skills, which
most producers, shopkeepers and farmers do not possess. It is important that greater
• Research and development to identify more suitable strains, and to develop better
production technology and quality control methods has to be increased greatly. The
money saved through the abolishment of various grants and subsidies should be
invested in these R&D programmes.
Acknowledgements
The study was funded by the Agricultural Economics Research Center, University of
Delhi. The author is grateful to Professor Prem Vashishtha, Director, Agricultural
Economics Research Center, University of Delhi for his support to the study. The views
expressed in the paper, however, are solely the responsibility of the author.
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Received: 1 May 2008 / Accepted: 28 November 2008 / Published online: 14 December 2008
Ó Springer Science+Business Media B.V. 2008
Abstract Heat-treated animal bone char (ABC) has measured soil properties to predict the potential for
not previously been evaluated for its potential as a ABC dissolution in a soil. Dissolution of P from GPR
phosphorus (P) fertilizer. ABC, Gafsa phosphate rock correlated with soil pH and exchangeable acidity. In
(GPR) and triple superphosphate fertilizer (TSP) comparison with GPR, ABC was a better source of
were incubated in 12 soils. Dissolved-P was assessed available P, assessed by Olsen-P. In most soils, ABC
by extraction with NaOH and bioavailability with the increased Olsen-P immediately after application,
Olsen extractant. The rate of P dissolution from ABC including soils of relatively high pH in which GPR
was described almost equally well by the Elovich and was ineffective. ABC is a P fertilizer of solubility
Power equations. After 145 days, the fraction of P intermediate between GPR and TSP.
dissolved ranged from 0 to 73% and to 56% for ABC
and GPR, respectively. The most important soil Keywords Available P Biochar
properties determining P dissolution from ABC were Fertilizer Phosphorus Phosphate rock
pH and P sorption. P dissolution was not significant at
soil pH [6.1 (ABC) and [5 (GPR) and the lower the
pH, the greater the Dissolved-P. Dissolved-P also
correlated positively and significantly with inorganic Introduction
P sorption, measured by the Freundlich isotherm and
the P sorption index of Bache and Williams (1971). It is probable that bones have always been regarded
Soil pH and P sorption index could be combined in as a valuable manure, and by about the end of the
multiple regression equations that use readily eighteenth century, their manurial value was attrib-
uted to phosphates (Smith 1959). Bone products
remain advocated and widely used in domestic
gardening (Royal Horticultural Society 2002). How-
ever, by the 1950s, for most commercial farming,
bone and P fertilizers derived from it were sup-
G. P. Warren (&) J. S. Robinson
Department of Soil Science, The University of Reading, planted by fertilizers made from mineral deposits
P.O. Box 233, Reading RG6 6DW, UK (Smith 1959). This lack of interest in bone as a
e-mail: g.p.warren@reading.ac.uk fertilizer for commercial purposes may explain the
observation that reliable data on the plant availabil-
E. Someus
Terra Humana Ltd, Széchenyi u. 59, ity of P from recycled products of P-containing
1222 Budapest, Hungary wastes such as sewage sludge, meat and bone are
123
168 Nutr Cycl Agroecosyst (2009) 84:167–178
123
Nutr Cycl Agroecosyst (2009) 84:167–178 169
Grass Fallow
Grass Fallow
were measured by the method of Robinson et al.
Veg/Grass
Vegetable
Vegetable
Vegetable
Vegetable
(1992). The P sorption index of Bache and Williams
Land use
Arable
Arable
Arable
Forest
Forest
(1971) was measured, being the quotient X/logC,
where X equals P sorbed (mg P 100 g-1 soil) and C
the P concentration in solution (lmol P l-1). Two
Ca (cmol kg-1)
21.96
26.45
13.88
2.84
3.95
0.29
1.14
1.24
3.02
6.83
1.05
comparable to the actual rate of added P used in the
incubation experiment. To measure the P sorption
(cmol kg-1)
7.91
1.23
1.92
3.13
5.37
5.41
35.80
37.19
12.53
21.89
CEC
P ¼ a Cb ð1Þ
pH buffering
12.84
18.02
10.73
24.33
37.03
7.51
8.85
8.8
12.0
23.2
14.4
13.6
17.0
11.7
37.3
12.7
21.7
30.0
170.2
8
68
52
92
20
14
75
17
17
18
8.3
2.4
4.7
18.8
78.7
26.4
25.9
46.1
40.2
31.6
53.0
16.1
(%)
Incubation procedure
Netherlands
Cameroon
Germany
Hungary
Hungary
Country
Zambia
UK
UK
UK
Rosemaund
Compost
Pwllpeiran
Misamfu
Neuhaus
Albenga
Szentes
Kiboko
Odja
Soil
123
170 Nutr Cycl Agroecosyst (2009) 84:167–178
Table 2 Phosphorus
Soil P sorption index (cg kg-1) Freundlich isotherm parameters
sorption properties
-1
of the soils P addition rate (mg kg ) a (mg kg-1) b (l kg-1)
300 1500
the dark in polyethylene containers with ventilation (RCF = 2,800g) to remove precipitated humic acid,
holes. Soil water content was maintained by occa- and the P concentration measured colorimetrically. In
sional addition of purified water to weight. At days 1, calculation of the results for P extracted by NaOH,
5, 13, 34, 70 and 145, soil samples were taken from allowance was made for P in the NaCl solution that
each replicate for Olsen P and P dissolution analysis. was entrained in the moist soil immediately before
For some soils, there were minor deviations from this addition of NaOH. Dissolved-P was defined as the
sampling plan to fit with the calendar. At the end of difference between treated soil and Control soil (the
the incubation period, a portion of the remaining soil mean value) for the P extracted by NaOH.
was air-dried at 30°C and ground to pass a 2-mm
aperture sieve prior to storage for additional analysis.
Description of dissolution rates for ABC
Dissolved-P in soil
The following equations with two fitted parameters
A two-step sequential extraction was performed are commonly used to describe the kinetics of soil
following the method of Mackay and Syers (1986). processes such as sorption and dissolution (Sparks
Soil (containing 0.8 g oven-dry mass) was weighed 1989):
into a pre-weighed polymer centrifuge tube (50 ml).
First order: Q ¼ a 1 ebT ð2Þ
NaCl solution (1.0 M, 40 ml) was added and the tube
shaken end-over-end for 30 min. Following centrifu- Elovich: Q ¼ a þ b ln (T) ð3Þ
gation (RCF = 500g), the supernatant was carefully
Powerequation: Q ¼ a Tb ð4Þ
decanted and the tube with moist soil reweighed.
NaOH solution (0.5 M, 40 ml) was added and the where Q is the quantity of product at time T in days,
tube shaken with a vortex mixer to re-disperse the and a and b are fitted parameters. In presentation of
soil. The sample was shaken end-over-end for 16 h, results, a and b are re-used in the different equations,
centrifuged (RCF = 2,800g) and the supernatant but this does not imply any relationship or connection
filtered (Whatman 42 filter). between the same parameter symbol used in different
P in the NaCl extract was measured colorimetri- equations. Dissolved-P was used for Q. The results
cally by the molybdenum blue and ascorbic acid were fitted by linear regression for the Elovich
method (Kuo 1996). An aliquot of the NaOH extract equation and by non-linear regression for First order
was neutralized with 1 M H2SO4, centrifuged and Power equations.
123
Nutr Cycl Agroecosyst (2009) 84:167–178 171
All statistical calculations were made with Genstat The addition of ABC produced an immediate signif-
(Lawes Agricultural Trust 2006). icant increase in Olsen-P after one day of incubation
in all soils except Albenga and Szentes (Table 4).
The increase, relative to the control, ranged from
Results 6.1 mg kg-1 (Hula) to 44.9 mg kg-1 (Whiteknights).
In most soils where ABC caused immediate Olsen-
ABC and Gafsa PR P increase, Olsen-P increased further over the incu-
bation period, and by the end of incubation the value
The ABC and GPR contained similar concentrations was changing little. In Szentes soil with ABC, Olsen-
of total P (13.4 and 12.5%, respectively). However, P remained unchanged, while in Albenga, Florasca
ABC contained very much more P in all extractable and Hula, Olsen-P declined (Table 4). In Florasca
forms; for example, 244 mg kg-1 water extractable P and Hula soils, ABC initially gave an increase in
compared with 42 mg kg-1 in GPR (Table 3). Olsen-P, but not after 145 days.
Organic C was a minor component (10.4%) of ABC. GPR gave an immediate increase in Olsen-P only
in Odja, Neuhaus, Misamfu and Whiteknights soils.
In the same four soils plus Pwllpeiran, there was a
significant increase in Olsen-P during incubation. In
Table 3 Properties of ABC and Gafsa PR
Albenga and Florasca, there were decreases in Olsen-
ABC GPR P during incubation with GPR, in parallel with those
Total P (%) 13.4 12.5 seen in those soils incubated with ABC.
Neutral ammonium citrate extractable P (%) 11.5 4.1 TSP caused a significant initial increase in Olsen-P
Olsen P (mg kg ) -1
1498 116 for all soils (Table 4), but the size of the increase
Water extractable P (mg kg-1) 244 42
differed between soils and for all TSP treated soils,
Total C (%) 12.50 2.13
Olsen-P was much less than the Control value plus
Organic C (%) 10.4 0.38
500 mg P kg-1. During incubation, Olsen-P declined
in all soils except Szentes and Whiteknights. This
Surface area (m2 g-1) 82.2 16.5
suggests that a substantial and variable portion of the
pH (water) 7.6 6.4
soluble P was sorbed in all soils. The net sorption was
Table 4 Olsen-P (mg kg-1) in soils after incubation without P and with ABC, GPR and TSP
Soil Day 1 Day 145
Control ABC GPR TSP Control ABC GPR TSP
123
172 Nutr Cycl Agroecosyst (2009) 84:167–178
Power
300
y = -0.6847x + 236.79
51.6
10.0
87.4
36.3
81.8
88.6
81.6
87.8
250 R 2 = 0.51
Table 5 Fitted parameters of the First order, Elovich and Power equations, used to describe Dissolved-P from ABC (mg kg-1) in relation to time (days) for eight soils
Olsen-P from TSP,
Elovich
150
50.1
10.8
86.2
39.7
84.3
84.1
81.9
84.8
100
50
First order
0
29.0
23.6
42.7
39.3
73.3
80.5
60.0
55.0
0 100 200 300
Freundlich parameter a
0.0422
0.0577
0.0166
0.0616
0.0423
0.0332
0.0254
0.0214
Fig. 1 Olsen-P derived from TSP applied at 500 mg P kg-1, at
s.e.
Day 145 of incubation, in relation to Freundlich parameter a of
the soil P sorption isotherms
0.1702
0.0899
0.1660
0.1740
0.2973
0.3119
0.1963
0.2117
estimated by the difference between TSP and Control
b
treatments for Olsen-P. Hula and Pwllpeiran soils
5.12
4.70
5.65
9.56
7.92
3.37
10.7
10.3
showed the greatest TSP sorption. It was correlated
s.e.
significantly with P sorption, assessed by the two P
sorption indices, and highly significantly with Fre-
31.0
22.2
87.5
39.9
60.4
56.7
33.6
118.9
undlich sorption isotherm parameter a (Fig. 1).
1.90
1.53
2.19
3.47
4.56
4.42
1.29
4.54
ABC dissolution rate
s.e.
for eight soils (Table 5). For Kiboko soil, there was
Elovich parameters
4.22
11.4
14.9
14.5
14.9
s.e.
4.73
2.77
9.89
7.87
4.35
16.5
15.1
18.8
s.e.
83.6
75.6
170.5
229.2
240.3
292.8
Rosemaund
Pwllpeiran
soil).
123
Nutr Cycl Agroecosyst (2009) 84:167–178 173
Table 6 Dissolved-P from ABC, GPR and TSP after 145 days’ incubation, as a percentage of P applied (PD145)
Soil PD145 Effect of P source on soil pH (water)
ABC GPR TSP ABC GPR TSP
For GPR, PD145 was significant in only four soils properties could be masked for those soils of pH \7.
(Table 6). Compared with ABC, a lower pH was Therefore, the correlations to assess factors influencing
required for P dissolution, less than 5.03 (Misamfu ABC dissolution were based only on the eight soils
soil). Both ABC and GPR caused significant with measurable P dissolution from ABC, comprising
increases in pH for seven of the soils (Table 6). the seven with significant PD145, plus Kiboko.
These soils were the same seven where PD145 for Although the PD145 for Kiboko soil was not signif-
ABC was significant. TSP normally lowered pH. icant, the fitted dissolution curves did demonstrate
The relationships of PD34 and PD145 with pH significant P dissolution on average (rate parameter a).
appeared curved because there are four soils with high
pH values and non-significant P dissolution, while at Correlations between ABC dissolution and soil
soil pH less than about 7.0, the relationship between pH properties
and PD145 was much closer to linear (Fig. 2). It was
considered that if P dissolution did not occur above Significant inverse correlations were found between
about pH 7, then the weaker influence of other soil PD34 and PD145, and soil pH (Table 7). Significant
positive correlations were found between PD34 and
80 PD145, and the following properties relating to P
70 sorption: Freundlich parameters a and ab, and P
60 sorption index at both rates of P addition. Fitted
50 parameter a of the Power equation for dissolution rate
PD145 (%)
123
174 Nutr Cycl Agroecosyst (2009) 84:167–178
Table 7 Extract from the matrix of correlation coefficients parameters a and k for dissolution of ABC, and soil properties,
between dissolved-P at 34 and 145 days (PD34 and PD145 for the eight soils with measurable P dissolution from ABC
respectively) for ABC, PD145 for GPR, power equation
GPR ABC ABC
PD145 PD34 PD145 Power Eq-a Power Eq-k
123
Nutr Cycl Agroecosyst (2009) 84:167–178 175
50
40 ð8Þ
30 It shows that dissolution of 3 mol of P require 7
20 mol of acidity (H?); therefore 500 mg kg-1 of P
10 would require (7/3) 9 (500/30.97) = 37.7 mmol kg-1.
0 PD145 shows that 68% of ABC was dissolved
0 20 40 60 80
(Table 6), thus consuming 25.6 mmol kg-1 acidity,
Fitted Value
while the measured consumption was 32.2 mmol
Fig. 3 Multiple regression equation describing PD145 (ABC kg-1. Given that there is substitution of both cations
dissolved at 145 days) in relation to soil pH and soil P sorption and anions in the ABC, and other components such as
index, for eight soils with significant P dissolution. Fitted carbonate that may consume acidity, this is considered
value = 72.1 - 12.2 9 pH(KCl) ? 2.22 9 Pindex-300
to be reasonable agreement. Thus the acidity required
to dissolve ABC was provided largely by the inorganic
PD145½GPR ¼ 0:781 PD145½ABC 9:34 ð7Þ exchangeable acidity.
123
176 Nutr Cycl Agroecosyst (2009) 84:167–178
Soil acidity was clearly a major constraint on P Comparison of P dissolution from ABC and GPR
dissolution from ABC. This is shown by (i) the
significant correlations of PD145 with soil pH In general, initial soil pH is a good predictor of PR
(Table 7), (ii) the increases in soil pH when P dissolution (Rajan et al. 1996), and we found the
dissolution occurred from ABC (Table 6), (iii) the same applied to dissolution of ABC. An approximate
significant correlation of dissolution rate parameter a cut-off pH value could be identified above which P
with exchangeable acidity and Al, and (iv) the dissolution was insignificant, for GPR ([5.03) and
consumption of exchangeable acidity in Whiteknights ABC ([6.14). For both ABC and GPR, the closest
soil (Table 8). correlations with soil properties were with pH, while
Dissolution of calcium phosphates such as ABC the correlation of GPR dissolution was less close with
releases Ca and H2PO4- into soil solution (Eq. 8), P sorption (Table 7). For the eight soils with signif-
and therefore the reaction will not proceed if soluble icant ABC dissolution, the relationship between soil
Ca and H2PO4- concentrations rise too far. A sink for pH and PD145 approximated to linear below pH 7
P dissolved was also an important soil property that (Fig. 2), and other linear relationships between soil
influenced P dissolution from ABC. This was shown pH and PR dissolution have been found, e.g., in acid
by significant correlations of PD34 and PD145 with New Zealand soil (Bolan and Hedley 1990). Corre-
the two P sorption indices and the ‘‘extensive’’ lation of P dissolution parameters for North Carolina
parameter a of the P sorption isotherms (Table 7). PR in 16 Colombian acid soils showed significant
The latter relates to the P sorption capacity of the soil effects of P sorption, pH and exchangeable Al (Chien
(Holford 1982), whereas the parameter b is an affinity et al. 1980b). The same effects were found in this
parameter (Holford 1982) for P sorption, and was not work with GPR, but Chien et al. (1980b) found
correlated with the extent of ABC dissolution, again additional correlations with clay and organic matter,
suggesting that the capacity of the soil to sorb which were not found in our group of soils. However,
released P is an important influence. Dissolution of we can conclude that the generally established
PR has been shown to be positively affected by the controlling principles for P dissolution from PR also
size of Ca sink (Robinson et al. 1992), but there apply to ABC.
was no significant correlation of PD145 with CEC
or exchangeable Ca, either alone or in multiple Agronomic effectiveness of ABC
regressions. This suggests that the sink for Ca was not
an important factor in assisting P dissolution from Recent data on the availability of P to plants from
ABC. modern recycling products are rare (Romer 2006).
After addition of 500 mg kg-1 soluble P as TSP, Studies show that products such as MBM (meat and
the P remaining extractable as Olsen-P was lower in bone meal), steamed bone meal and bone chips give P
soils with higher P sorption as expected (Fig. 1). This responses to pot and field grown crops (Romer 2006;
shows that soluble P released by dissolution from Jeng et al. 2006; Klock and Taber 1996). ABC is
ABC is sorbed in the soil, reducing its plant manufactured using much higher temperatures (ca.
availability, but providing a bigger sink and therefore 400°C) than the previously mentioned materials and
encouraging P dissolution. The complementary contains less organic matter. It was therefore
nature of the P sink with acidity is illustrated by the expected to have different surface properties and
very close multiple correlation of the two with PD145 different dynamics of dissolution and availability
(Eqs. 5, 6). when compared with PR and the above-mentioned
The two multiple correlations of PD145 with pH materials.
and P sorption (Eqs. 5, 6) suggest that relationships Olsen-P is a widely accepted laboratory index of
could be obtained to predict the likely extent of ABC the plant-available P in soil, and it is useful in both
dissolution in a soil from its known properties. acid and calcareous soils (Kuo 1996), a particular
Equation 5 gave the closer correlation, but Eq. 6 uses advantage in the present work where a wide soil pH
variants of the measurements that are more com- range was intended. At the end of the incubation
monly in routine use for other purposes, and so are period, the soils where significant P dissolution from
better suited for predictive use. ABC occurred (Table 6) were the same ones that
123
Nutr Cycl Agroecosyst (2009) 84:167–178 177
gave significant increases in Olsen-P (Table 4), mineralogical and surface properties of ABC and P
showing that P dissolution is a guide to the P dissolution from it.
availability to plants and that ABC will be an The above conclusion implies that the knowledge
effective P fertilizer in many soils. of the soils and circumstances when PR is useful as a
When P dissolution occurred, the majority took fertilizer applies also to ABC. However, in a direct
place in the first 20 days. Because the mobility of P in comparison with GPR, which is well-characterised
soil is low, the early availability of P is essential for and widely accepted as a relatively soluble PR, ABC
proper crop development (Hedley et al. 1995). ABC was much better in providing available P, as assessed
showed a clear benefit to Olsen-P over GPR for most by the Olsen method. It could even supply some
soils (Tables 4, 5). In two soils, Florasca and Hula, available P immediately after application to soils of
ABC improved Olsen-P at Day 1 although not at Day high pH, in which GPR was ineffective. Therefore,
145, and these soils were high pH soils where GPR ABC is predicted to have a wider range of application
was completely insoluble. Thus, for most soils, ABC than PR, so that the soils for which it is suitable and
provides a limited but immediately available P pool rates of ABC addition need to be assessed under field
in soil, combined with further P release thereafter, a conditions. Because of its apparent potential as a P
pattern of release that appears well timed to suit crop fertilizer, field trials are now in progress.
requirements. This pattern is different to the one for
TSP, where Olsen-P starts at a much higher concen- Acknowledgements This work was financially supported by
the European Union, Framework VI (Contract no. FOOD-CT-
tration than with ABC and then declines because of 2005-514082). We thank the anonymous reviewers for their
the reaction of dissolved phosphate with soil helpful comments.
(Table 4). However, it should be noted that for
slowly-soluble fertilizers, Olsen-P gives a measure of
the availability of immediate reaction products only References
and underestimates plant-available P (Menon and
Chien 1995; Saggar et al. 1992). Thus in comparison Anderson JM, Ingram JSI (1993) Tropical soil biology and
with TSP, plant-available P from ABC may be better fertility. A handbook of methods. CABI, Wallingford
Bache BE, Williams EG (1971) A phosphate sorption index for
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1979.tb00983.x
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123
Oil Mallee charcoal properties
CEC meq/100g
volatiles%dry
ash%dry
fixed C%wet
fixed C%dry
s.area m2/g
0 20 40 60 80 100
%
1500
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
+340 kg/ha
2000
grain yield, kg/ha
1500
Pindar
1000
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
18% yield increase with half rates of soluble fertiliser at 6 t/ha char
mineral plus microbes
2500
2000
+640 kg/ha
grain yield, kg/ha
1500
1000
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
46% yield increase with at least 1.5 t/ha char added to the mineral fertiliser
values of yield increases
yield banded broad acre value ($/ ha) for carbon
Trial site# benefit charcoal equivalent wheat at value
and fertiliser kg/ha kg/ha
kg/ha t/ha charcoal carbon $150/t $250/t $/kg C#
1. 100 kg/ha
mineral+1 640 1.5 250 56 96 160 2.84
1. 30 kg/ha
soluble 2 344 6.0 1000 225 52 86 0.38
2. 110 kg/ha
soluble 3 76 6.0 1000 225 11 19 0.08
3. 110 kg/ha
soluble* 83 3.0 620* 140 12 21 0.15
#
wheat at $250/t
2.4
2.2
Pindar
grain yield, t/ha
2.0
1.8
1.6
1.4
1.2
1.0
10 15 20 25 30 35 40
grains per head
50
45
Pindar
root colonisation; flowering, %
40
at flowering
35
30
25
20
15
10
0
0 1 2 3 4 5 6 7
deep banded charcoal, t/ha
3
30 6
0
6
Grains per head
25
0 3
6 3
20 Pindar
0
at flowering
15
10
0 5 10 15 20 25 30 35 40 45 50
root colonisation September %
30
25
SYMBIOTIC ?
2
biomass at tillering, g/m
20
15
PARASITIC ?
10
0
0 1 2 3 4 5 6 7
banded charcoal, t/ha
6 "Bungadale", Kalannie , WA
location
• Mostly winter rain
WESTERN AUSTRALIA from May to October
ALLEY planting
potential
~10 Mt/yr biomass
from Ogawa, M. 1994.Symbiosis of
People and Nature in the Tropics.
Farming Japan Vol.. 28 – 5, p10 21.
plant
root
Symbiotic
fungi (AM)
mineral
particle
THE OIL MALLEE INDUSTRY
processing Mallee
for eucalyptus oil
OIL DISTILLATION
HARVESTING
Pyrolysis with an open pan ‘Moki’ method
at Kalannie by Shea, Stanley and Okimori
March 2005; air temp. = 40oC+!
Yasuyuki Okimori
wood charcoal (Jarrah) mallee charcoal (‘05 trials)
volatiles%dry
ash%dry
fixed C%wet
fixed C%dry
s.area m2/g
0 20 40 60 80 100
%
1500
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
+340 kg/ha
2000
grain yield, kg/ha
1500
Pindar
1000
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
18% yield increase with half rates of soluble fertiliser at 6 t/ha char
mineral plus microbes
2500
2000
+640 kg/ha
grain yield, kg/ha
1500
1000
500
0
0 1 2 3 4 5 6 7
rate of deep banded charcoal, t/ha
46% yield increase with at least 1.5 t/ha char added to the mineral fertiliser
values of yield increases
yield banded broad acre value ($/ ha) for carbon
Trial site# benefit charcoal equivalent wheat at value
and fertiliser kg/ha kg/ha
kg/ha t/ha charcoal carbon $150/t $250/t $/kg C#
1. 100 kg/ha
mineral+ 1 640 1.5 250 56 96 160 2.84
1. 30 kg/ha
soluble 2 344 6.0 1000 225 52 86 0.38
2. 110 kg/ha
soluble 3 76 6.0 1000 225 11 19 0.08
3. 110 kg/ha
soluble* 83 3.0 620* 140 12 21 0.15
#
wheat at $250/t
2.4
2.2
Pindar
grain yield, t/ha
2.0
1.8
1.6
1.4
1.2
1.0
10 15 20 25 30 35 40
grains per head
50
45
Pindar
root colonisation; flowering, %
40
at flowering
35
30
25
20
15
10
0
0 1 2 3 4 5 6 7
deep banded charcoal, t/ha
3
30 6
0
6
Grains per head
25
0 3
6 3
20 Pindar
0
at flowering
15
10
0 5 10 15 20 25 30 35 40 45 50
root colonisation September %
30
25
SYMBIOTIC ?
2
biomass at tillering, g/m
20
15
PARASITIC ?
10
0
0 1 2 3 4 5 6 7
banded charcoal, t/ha
5MW plant = $6.2M over 20 years; est. Bell and Bennett (2002)
Ogawa and Okimori (2004)
Ogawa and Okimori (2004)
A BENEFICIAL SYSTEM?
THANKYOU
Sylvain Pottier
Yasuyuki Okimori and Makoto Ogawa of
Kansai Environmental Engineering Centre,
Kansai Electric Co. Ltd and General
Environmental Technos Co., Ltd. and the
Oil Mallee Company for financial support
Ausplow Ltd for the use of their plot
airseeder. Andrew Donken
Victor Dodd and Doug Cail
Dave Gartner, Ben Parkin and Chris Gazey
United Farmers Cooperative and Hans
Schoof for soil testing and interpretation.
Stephen Davies, Bill Bowden, John Bartle,
and Tony Vyn for field advice and
assistance.
CSIRO PUBLISHING
www.publish.csiro.au/journals/ajea Australian Journal of Experimental Agriculture, 2007, 47, 1377–1382
Abstract. About 0.3 million t/year of composted garden organics (CGO) including mulches and soil conditioners are
produced annually in New South Wales, Australia, although only a small proportion of this material (<4%) is used in
agriculture. A lack of information on product characteristics and agronomic performance has limited the development of
agricultural markets for CGO products. These CGO products are the coarse and fine fractions separated by screening after
composting. This paper presents the results of a survey of CGO mulches and soil conditioners (unblended or blended with
a mixture of other organic materials including biosolids, animal manures and paper), which are commercially produced in
the metropolitan areas of New South Wales and assesses their agronomic and soil amendment values in terms of chemical
and biological properties. It also evaluates the short-term effects of applying increasing rates (0, 25, 50 and 100 t/ha) of
selected composted soil conditioners on radish growth in a pot experiment.
The mulch products had low nutrient concentrations but had high carbon (C) contents (mean C = 45%) and C/Nitrogen
(N) ratios (mean C/N = 72) and are most suitable for use as surface mulch. The unblended soil conditioners were low in
nutrients, particularly N (average total N = 1.0%, range 0.9–12%), and had lower and variable C contents. The pot trial
results indicated lack of growth response of radish at application rates up to 100 t/ha of unblended soil conditioners from
garden organics. The blended soil conditioners were more variable in quality and as confirmed by pot trial results produced
highly variable plant responses. The high variability in product quality and performance of the soil conditioners,
particularly the blended products might be related to the source and type of blending material as well as the composting
conditions used in the manufacturing process.
These results highlight the need to improve compost quality and consistency and the need for further research to
advance understanding of the benefits using CGO in terms of improving soil quality, crop productivity and net economic
returns to growers.
Introduction
Composts produced from plant and animal residuals have been 2004). After composting, the product is usually screened into
used by farmers worldwide for many hundreds of years to coarse and fine fractions, to produce mulches and soil
increase crop productivity and improve soil quality but they are conditioners, respectively.
not typically used as a component of Australian agricultural Most (87%) of the recycled organics generated in the Sydney
production systems. However, Australian farmers are metropolitan area are consumed in the urban amenity market
increasingly seeking alternatives to conventional inputs to segments including landscaping, and domestic garden
provide plant nutrients and improve soil health as indicated by applications (DEC 2004). However, the urban amenity market is
the increasing interest in the use of organic fertilisers instead of approaching saturation (WMAA 2005), whereas only ~4% of
inorganic fertilisers. the CGO are currently used in agriculture (DEC 2004). Given
Across Australia, government legislation (Resource NSW the large area of arable agricultural land in NSW
2001; Victorian Consolidation Legislation 2005) and strategies (>100000 km2; ABS 2001) the size of the agricultural market is
(Resource NSW 2003; Zero Waste SA 2005) focus on diverting virtually unlimited.
materials from landfills and the beneficial re-use of these As a prerequisite for developing agricultural markets for
materials. For example, in New South Wales (NSW), Australia, composts, there is a need to understand the characteristics of
over 600000 tonnes of garden organics, such as grass clippings, CGO and demonstrate their agronomic value to farmers.
prunings and other vegetation, are collected from households However, little information is available on the quality and
and municipal areas each year and composted to produce agronomic performance of the CGO currently being produced
~0.3 m t/year of composted garden organics (CGO) (DEC in NSW.
The objectives of this paper are: (i) to present the results of a manure and paper pulp and represented the range of materials
survey of CGO being commercially produced in the commonly used in compost manufacturing in NSW. All the
metropolitan areas, particularly in the Sydney region; (ii) to compost samples were brought to ~40% moisture content and
assess their agronomic and soil amendment values in terms of left at room temperature for 4 days before application.
physical, chemical and biological properties; and (iii) to The soil used for the pot trial was collected from 0–10 cm of
evaluate the short-term performance of selected soil a grey Dermosol (Isbell 1996) located at the Centre for Recycled
conditioners in a pot experiment. Organic in Agriculture, near Camden (70 m Australia Height
Datum at 34.07536°S, 150.6956°E), NSW. The site had a long
Materials and methods history of cropping and cultivation but was under lucerne pasture
Survey of CGO at the time of sampling. The soil properties were: pHCa (4.5);
A survey of 13 composting facilities in the Sydney region and organic C (12.9 g/kg); extractable P (21 mg/kg); water content
other major metropolitan areas of NSW was conducted in 2004. field capacity (–10 kPa) (0.28 kg/kg); clay content (260 g/kg).
All the facilities surveyed employed open-windrow systems, the
Treatments and experimental design
dominant form of composting in most parts of Australia
(Wilkinson et al. 2002). At each facility, finished compost Treatments involved 10 soil conditioners and four rates of soil
products that were ready for market were collected. Composite conditioner application, namely 0, 25, 50 and 100 t/ha on an
samples (10–20 kg) of composted soil conditioners and mulches oven dry basis. The experiment followed a randomised complete
were obtained by shovelling 1–2 kg of compost from 10 random block design with four replications. Pots (115-mm internal
positions in the standing pile into plastic bags. The composite diameter and 100-mm tall) with individual trays were used. The
samples were thoroughly mixed and stored at 4°C before analysis. quantity of oven dry soil conditioners equated to 0, 25, 50 and
In total, nine CGO mulches, 10 CGO soil conditioners and 100 g/pot for the four application rates, respectively. 900 g of
12 blended CGO soil conditioners were collected and studied in oven dry equivalent of the screened soil was packed into each
this research. Soil conditioners refer to the fine compost pot. The appropriate amount of soil conditioner was then added
fraction (<8–10 mm) produced from garden organics as the only to the respective pot and thoroughly mixed. The individual pots
feedstock. Blended CGO soil conditioners are fine compost were then watered to field capacity (28% by weight) and left for
fraction produced from either co-composting a mixture of 24 h in the glasshouse before sowing.
garden organics and other organic residuals, such as biosolids, Ten radish seeds (Raphanus sativus L. cv. Long Scarlet) were
poultry litter and cattle feedlot manure or mixing CGO soil sown in each pot and these were thinned to five after plant
conditioners with other organic residuals. emergence. The pots were placed on four benches, each of
which represented an experimental block. All of the pots were
CGO characterisation randomised within each block. During the experiment, all the
The samples of mulches and soil conditioners were analysed for pots were maintained at approximately field capacity and
a range of chemical, physical and biological properties. watered by hand on a regular basis.
Immediately after sampling, moist samples were analysed for After 26 days, the radish plants were harvested and the fresh
pH, electrical conductivity, ammonium, nitrate and soluble weight of both the tops and roots recorded. The harvested plants
phosphorus (P) concentration following the procedures were dried at 60°C to constant weight and re-weighed to
described in Standards Australia (2003). The CGO soil determine dry weight.
conditioners were also tested for phytotoxicity and microbial
activity. The phytotoxicity bioassay involved germinating radish Statistical analyses
seeds on a sample of soil conditioner and assessing early root The different properties of the compost products were compared
growth against a minimum length requirement of 60 mm using 1-way ANOVA in GENSTAT (VSN International Ltd 2003).
(Standards Australia 2003). Microbial activity was measured For the pot trial, results of both fresh weight and dry weight of
using the Food and Drug Administration (FDA) enzymatic test
(Schnurer and Rosswall 1982). Table 1. Descriptions of the blended and unblended soil conditioners
Subsamples of mulches and soil conditioners were dried and derived from composted garden organics (CGO) used in the pot
ground (<2 mm) and analysed for total carbon (C), organic experiment
nitrogen (N), total sulfur (S), total P, pH, electrical conductivity
(EC), total copper (Cu), total zinc (Zn) and total iron (Fe). pH Sample no. Type of conditioner Description
and EC were determined on 1 :5 sample/water extract following 2 Soil conditioner CGO
Rayment and Higginson (1992). Total C, N and S were 3 Soil conditioner CGO
determined using Leco combustion (Rayment and Higginson 6 Soil conditioner CGO
1992). Total P, total Cu, total Zn, total boron and total Fe were 28 Soil conditioner CGO
determined using an inductively coupled plasma mass 1 Blended soil conditioner CGO/biosolids
spectrometer after acid digestion (USEPA 1996). 5 Blended soil conditioner CGO compost/poultry
litter/cow manure
Pot experiment 11 Blended soil conditioner CGO/biosolids
Four soil conditioners and six blended soil conditioners were 14 Blended soil conditioner CGO/paper compost
16 Blended soil conditioner CGO/poultry litter
used in the pot experiment (Table 1). The blended soil
17 Blended soil conditioner CGO/poultry litter
conditioners contained biosolids, poultry litter, cattle feedlot
Agronomic value of composted garden organics Australian Journal of Experimental Agriculture 1379
the radish using different soil conditioners and rate of Product variability
application were analysed using 2-way ANOVA. Differences While the C content of the mulches was fairly uniform (range
between treatments were statistically significant at 5% 41–47%, CV = 4.5%), nutrient concentrations (total N and total
probability unless otherwise stated. Product variability was P) were more variable (CV >20%) (Table 2). Total N
assessed by examining the ranges as well as coefficients of concentration in the mulches varied more than 2-fold (range
variation (CV) of the different chemical parameters of the 0.5–1.0%), resulting in a similar magnitude of variation in the
different categories of composting products. Linear regression C/N ratio (range 41–104). Higher variability was found in the
analysis was also undertaken in GENSTAT to determine; soluble/available nutrients, namely, soluble P and mineral N
(i) whether radish dry weight was correlated with any of the (CV >50%).
compost chemical parameters measured; and (ii) correlation, if Compared with the mulches, soil conditioners were more
any, between results of FDA test and phytotoxicity bioassay. variable in C content (15–32%, CV = 25.8%). While the C
Results content of the blended soil conditioners was similar to those of
the unblended soil conditioners, they were highly variable with
Product quality respect to most of the chemical parameters measured (Table 2).
Apart from size grading, the mulches had very different For example, mineral N concentration ranged from 1.3 to
properties compared with the soil conditioners (Table 2). The 530 mg/kg (Table 2). The results from the phytotoxicity
mulches had lower total N, total P, total Ca and total magnesium bioassays (Table 3) showed that despite similar mean values, the
concentrations but higher C and C/N than the soil conditioners. blended soil conditioners were more variable than the unblended
Mean C content of the mulches was 44.6%, which is nearly soil conditioners (CV 65.8 v. 13.7%; Table 3). In fact, 42% of
twice that of the soil conditioners. Mean C/N of the mulches the blended products had root length <60 mm, the critical value
was 71.7 compared with 25.5 of the soil conditioners. below which the medium is classified as phytotoxic (Standards
Comparing the two categories of soil conditioners revealed Australia 2003). In contrast, similar CV was found for the FDA
the blended soil conditioners had higher average EC, mineral N results of the two categories of soil conditioners.
and total S (Table 2) than the unblended soil conditioners. They
were also higher in heavy metals, as indicated by the Zn and Cu Pot experiment
concentrations in Table 2. Mean FDA values as well as CV were For the soil conditioners, no significant changes in fresh weight
similar between the two groups of soil conditioners (Table 3). of radish harvested 26 days after sowing with increasing
Similarly, mean root length, as a measure of phytotoxicity, was application rates up to 100 t/ha were observed (Fig. 1). In
not significantly different between the unblended CGO soil contrast, radish fresh weight increased in response to increasing
conditioners and the blended products. application rate in five out of the six blended soil conditioners
Table 2. Mean, range (in parentheses) and coefficient of variation (CV%) of basic chemical properties total elemental composition of
mulches, soil conditioners (SC) and blended soil conditioners (blended SC) produced from composted garden organics in the
metropolitan areas of New South Wales
Within rows, mean values followed by different letters are statistically different (P < 0.05)
Table 3. FDA and phytotoxicity tests of soil conditioners (SC) and blended soil conditioners
(blended SC) produced from composted garden organics in the metropolitan areas of New South Wales
Mean values in the same row followed by different letters are statistically different (P < 0.05)
FDA (µg fluorescein/g soil.min) 25.6a (10.7–40.1) 22.7a (8.9–52.9) 44.1 58.6
Root length (mm)A 98a (78–115) 63a (16–112) 13.7 65.8
AThe phytotoxity test using radish plant roots following Standards Australia (2003).
evaluated. The only exception was the blended soil conditioner The nature of radish dry weight production in response to
containing paper pulp (no. 14), which did not affect radish fresh increasing application rates of unblended and blended soil
weight at any rate of application compared with the nil treatment conditioners was similar to that observed for fresh weight
(Fig. 1a). It had the lowest total N concentration (0.5%) and production (Fig. 1). Regression of dry weight with mineral N,
negligible mineral N (1.3 mg/kg; Table 2). Three of the blended total N and C/N ratio of the soil conditioners all resulted in
soil conditioners (no. 1, 11 and 17) showed continuing increases statistically significant correlation coefficients. Dry weight of
in radish fresh weight with increasing application rates. Two of radish was found to be positively correlated with mineral N and
the samples (no. 5 and 16) showed increases up to 50 t/ha and total N but negatively correlated with C/N ratio. The highest
then remained unchanged at higher application rates. Both had correlation coefficient (r2 = 0.788) was obtained in the case of
high mineral N concentration but were found to be phytotoxic C/N ratio. The equation is:
(root length <20 mm long). DW = 4.931 – (0.135 × CN) (r2 = 0.788, n = 10, P < 0.001) (1)
where DW is dry weight of radish at harvest and CN is C/N ratio
of the soil conditioners. Therefore, dry matter production of
35 11
(a) radish was negatively related to C/N ratio of the soil
16 conditioners.
1
Fresh top weight (g/pot)
30
5
Discussion
25
17 The mulches had low nutrient concentrations (e.g. mean mineral
20 n = 27 mg/kg) and high C/N ratios (mean 72) suggesting they
are unlikely to be a source of nutrients for growing plants.
15 However, the mulches are likely to be suitable as compost
blankets for controlling weeds, conserving water and protecting
10 2 the soil surface against erosion (DEC 2005).
6
14 Compared with the other organic amendments (cow manure,
5 3
28
N = 1.5%, P = 0.5%, potassium (K) = 1.2%; blood and bone,
N = 5.3%, P = 5.2%; poultry manure, N = 3.1%, P = 2.5%,
0
K = 1.6%; sewage sludge, N = 2.0%, P = 1.0% (Burgess 1993)),
16
3.5 (b) soil conditioners produced from garden organics as the only
11
feedstock were generally low in total N (1%), P (0.07%) and K
3.0 1
Dry top weight (g/pot)
17
(0.5%). In fact, average total N of the soil conditioners was less
2.5
5 than a third of that of the poultry manure (Table 2). According
to Verdonck (1998), the total N of whole green compost (before
2.0 screening) ranged from 0.6 to 0.8%. Cook et al. (1998) used a
green waste compost with a total N concentration of 1% to grow
1.5 2 barley and found that the only significant yield increase was
6 observed at the highest rate of compost application (150 t/ha).
1.0 14 The low nutrient concentrations in the soil conditioners of our
3
study can be partly attributed to the nature of the feedstock,
0.5 28 which consisted of grass clippings and tree prunings. The mean
C/N ratio for the unblended soil conditioner was 25.5, which is
0 20 40 60 80 100 higher than the recommended optimal C/N range of 15 to 20 :1
for mature compost (Verdonck 1998). Composts with C/N ratios
Application rate (t/ha)
above 25 to 30 :1 usually immobilises inorganic N (Sullivan and
Fig. 1. (a) Fresh weight and (b) dry weight of radish tops (g/pot) in Miller 2001). The pot trial results confirmed the low nutrient
response to increasing application rates (0, 25, 50 and 100 dry t/ha) of soil availability of the soil conditioners produced from garden
conditioners () and blended soil conditioners () produced from organics alone and their unsuitability as soil amendments when
composted garden organics. applied as sole source of fertilisation. The significant reverse
Agronomic value of composted garden organics Australian Journal of Experimental Agriculture 1381
relationship between dry matter of radish plants and C/N ratio 2002). However, the unblended and blended CGO soil
(Eqn 1) suggested the usefulness of the ratio as an indicator of conditioners evaluated in our survey had mean C concentrations
compost maturity. Garcia et al. (1992) also suggested that C/N of 25 and 21%, respectively, and some were as low as 14–15%,
is a good indicator of maturity for composts made from which was much lower than expected. This suggests inorganic
feedstock of high C/N ratio. materials, such as sand and clay were somehow enriched during
The FDA test is a measure of microbiological activity based processing. If these products are to be promoted for use as a
on enzymatic activities (Schnurer and Rosswall 1982). source of organic matter, then the total C concentrations will
Recently, the test has been evaluated as an indicator of need to be increased. The long-term benefit of CGO soil
microbiological activity and hence of compost stability during conditioners in improving soil quality of organic matter
composting process, with conflicting results (Garcia-Gomez impoverished soil needs to be demonstrated in field experiments.
et al. 2003; Saviozzi et al. 2004; Ntougias et al. 2006). While The generally higher variability of the blended soil
Garcia-Gomez et al. (2003) concluded that the FDA test could conditioners compared with the unblended soil conditioners
be used in place of respiration rate as a measure of stability reflected the variety of materials used for blending. The survey
during composting of olive wastes, results of Saviozzi et al. results further highlighted how the type of blending material
(2004) for composting of urban wastes indicated that FDA can influence the properties, such as nutrient status, and
values did not alter during the entire composting process and as agronomic performance of the final product. For example, the
such was not a sensitive indicator of stability compared with the blended soil conditioners containing biosolids were higher in N
standard respiration test. In the present study, similar FDA and heavy metals than those containing other organic residuals.
results between the two categories of soil conditioners The pot trial results emphasised that additional effort is still
suggested that they had similar level of microbiological activity, required to improve product consistency, given that the soil
even though 42% of the blended soil conditioners were found to conditioners containing the same blending material
be phytotoxic as measured by the root length bioassay test. (e.g. poultry litter in no. 16 and 17) did not perform equally,
Linear regression analyses indicated that the FDA results were with respect to increasing radish growth (Fig. 1). Compost
not significantly (P > 0.05) correlated with the root length quality and consistency can be improved by selecting feedstock
bioassay results and, therefore, suggested that it is unsuitable as and blending materials more judiciously, as well as controlling
an indicator of compost stability. Further research is needed to the composting process more carefully.
resolve the discrepancy and to assess the usefulness of FDA test Farmers will only buy CGO soil conditioners and mulches if
as an indicator of compost stability. there is a demonstrated value from using them, either through
The high variability in the chemical composition of the CGO improving soil quality and crop productivity or providing a net
compost products observed in this survey of NSW supported economic return. Such information is not available and limits
earlier reports from other parts of Australia (Wilkinson et al. the potential to develop agricultural markets for CGO.
2000; Wilkinson et al. 2002). Such high variability and, Consequently, further research is required to quantify the
therefore, uncertainty about the consistency of compost beneficial characteristics of these products and promote these
products has been identified as a barrier to market acceptance in benefits to farmers and the broader community.
Australian agriculture (Wilkinson et al. 2002). The variability in
the chemical composition of the CGO compost products is Conclusions
probably related to the differences in the composition of the Our survey of CGO commercially produced in the metropolitan
organic feedstock and the degree of maturity of the products. areas of NSW has revealed that mulches and soil conditioners
Garden organics can vary in total N concentrations depending have variable physical, chemical and biological properties.
on the proportions of leafy material, such as grass clippings and Similarly, our pot experiment revealed the short-term
more woody material like tree trunks and branches. This is agronomic performance of a selection of unblended and
influenced by several factors, such as the size of the operation, blended soil conditioners was inconsistent.
geographical location, season, rainfall patterns and method of Product variability can be reduced and product quality can be
garden organic collection (Wilkinson et al. 2002; Dorahy et al. improved by more careful selection of feedstocks and blending
2005). For example, more grass clippings are generated during materials, as well as better control of the composting process.
the summer months, which can lower the C/N ratio in composts Further research is required to quantify the benefits these
produced during this period. Degree of maturity is determined products have in terms of improving soil quality, crop
by the conditions and duration of the composting process (Chen productivity and net economic returns to farmers. These issues
and Inbar 1993). Immature compost products are often need to be addressed if viable agricultural markets for CGO are
biologically unstable and have the potential to reduce crop yield to be developed.
(Dick and McCoy 1993; Paulin et al. 2001). In our survey,
nearly half of the blended soil conditioners were found to be Acknowledgements
phytotoxic and, therefore, immature. Results of the pot trial Financial support provided by NSW Department of Environment and
highlighted the variable short-term plant responses, which were Conservation is acknowledged. We also thank the compost producers for
a direct reflection of the variability of the soil conditioners. their cooperation in undertaking this study.
CGO soil conditioners have the potential to play an important
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J. Plant Nutr. Soil Sci. 2008, 171, 893–899 DOI: 10.1002/jpln.200625199 893
Abstract
Leaching losses of N are a major limitation of crop production on permeable soils and under
heavy rainfalls as in the humid tropics. We established a field trial in the central Amazon (near
Manaus, Brazil) in order to study the influence of charcoal and compost on the retention of N.
Fifteen months after organic-matter admixing (0–0.1 m soil depth), we added 15N-labeled
(NH4)2SO4 (27.5 kg N ha–1 at 10 atom% excess). The tracer was measured in top soil (0–0.1 m)
and plant samples taken at two successive sorghum (Sorghum bicolor L. Moench) harvests.
The N recovery in biomass was significantly higher when the soil contained compost (14.7% of
applied N) in comparison to only mineral-fertilized plots (5.7%) due to significantly higher crop
production during the first growth period. After the second harvest, the retention in soil was sig-
nificantly higher in the charcoal-amended plots (15.6%) in comparison to only mineral-fertilized
plots (9.7%) due to higher retention in soil. The total N recovery in soil, crop residues, and grains
was significantly (p < 0.05) higher on compost (16.5%), charcoal (18.1%), and charcoal-plus-
compost treatments (17.4%) in comparison to only mineral-fertilized plots (10.9%). Organic
amendments increased the retention of applied fertilizer N. One process in this retention was
found to be the recycling of N taken up by the crop. The relevance of immobilization, reduced N
leaching, and gaseous losses as well as other potential processes for increasing N retention
should be unraveled in future studies.
Key words: biochar Brazil / carbon / nitrogen cycling / slash-and-burn / soil organic matter / Terra Preta
The sustained fertility of charcoal-containing Terra Preta and The charcoal derived from secondary forest wood and was
the frequent use of charcoal as a soil conditioner (Steiner considered rather as soil conditioner than fertilizer due to the
et al., 2004b) in Brazil provided the incentive to study the charcoal’s low nutrient contents (Tab. 1). It was manually
effects of charcoal application on N cycling. Charcoal acted crushed to particle sizes <2 mm. The applied 11 Mg ha–1
as an adsorber which reduced N leaching in previous pot corresponded to the amount of charcoal-C which could be
experiments (Lehmann et al., 2002, 2003), and charcoal produced by a single slash-and-char event of a tropical
additions proved to sustain fertility if an additional nutrient secondary forest on Xanthic Ferralsols in central Amazonia
source is given in a field trial (Steiner et al., 2007). Charcoal (Lehmann et al., 2002). The amount of C added with charcoal
plus fertilizer improved plant growth and doubled grain pro- was chosen as a reference value for adding the compost.
duction in comparison to the fertilizer without charcoal. Plant Compost was prepared from biomass of a secondary forest,
biomass production sharply decreased within 1 y when only fruit residues, manure, and kitchen waste. On February 3,
mineral fertilizer was applied, but could be maintained for a 2001, organic materials were mixed with hand hoes into the
longer period of time when OM was added. The authors pro- top soil (0–0.1 m) of the plots, and the first mineral fertilization
posed that charcoal can improve soil chemical, biological, was done on March 19, 2001 [30 N kg ha–1 as (NH4)2SO4,
and physical properties, but could not completely discern the 35 kg P ha–1 as simple superphosphate, 50 kg K ha–1 as KCl,
mechanisms of fertility enhancement (Steiner et al., 2007). and 2100 kg lime ha–1]. The fields were cropped twice (rice
Oryza sativa L. and sorghum Sorghum bicolor L. Moench)
Stable isotopes such as 15N can serve as valuable tracers to prior the second fertilization on April 16 (see Tab. 1 for treat-
study plant resource acquisition and as a means to understand ment description). All crop residues remained on the field,
how plants interact with their abiotic and biotic environments and only grains were removed. Sorghum was planted again
(Dawson et al., 2002). Therefore, our objective was to compare on April 18, 2002 in a density of 25 plants m–2 producing two
the effect of organic amendments such as charcoal and com- harvests by ratooning (July 21 and October 16, 2002). Only
post on retention of 15N-labeled mineral fertilizer in a highly these two harvests are subject of the present paper and
weathered Ferralsol under humid tropical field conditions. designated as 1st (HI) and 2nd (HII) harvest.
applied at a rate of 55 kg N ha–1 in April 2002 (second fertili- 2.4 Statistical analyses
zation). Additionally, 40 kg P ha–1, 50 kg K ha–1, and 430 kg
ha–1 of lime was applied. Soil and plant samples were taken Treatment effects were analyzed by one-way analysis of var-
at each harvest and analyzed for d15N. Only the top 0.1 m of iance (ANOVA). Significant treatment effects were detected
soil was sampled, this was also the depth down to which the using the Fisher’s LSD (last significant difference) test. Statis-
organic amendments were mixed. Two soil samples were tical analyses and figures were performed using SPSS 12.0
taken per plot to form one composite sample. Soils were air- (SPSS Inc.) and SigmaPlot 7.0.
dried and ground before isotope analysis. Representative
plant samples were taken from the entire crop by using the
center 1.4 × 1.4 m (49 plants) of each plot. Plant samples
3 Results and discussion
were dried at 70°C for 48 h and ground. While the soil C contents were significantly increased by the
organic amendments (CO and CC), the N values were only
The remaining fertilizer N in soil or plant biomass was calcu- significantly enhanced in comparison to the F plots if CO was
lated after Eq. 1 (Boutton, 1996). applied (Fig. 1). After the second harvest (HII), the N and C
contents on solely compost-amended plots (CO) did not differ
Nf d15 Nf Nf d15 Nc Y d15 NNPK , (1) from those receiving only mineral fertilizer. The OM-amended
and N-fertilized plots had significantly higher C and N con-
tents than the F plots. All organic amendments significantly
Nf = nitrogen content of biomass or soil in N-fertilized treat- increased the C : N ratio after the first harvest. This difference
ment, was even more distinct after the second harvest but only on
charcoal-containing plots (Fig. 1).
d15Nf = measured d15N value of biomass or soil in N-fertilized
treatment, Neither the N concentrations in the biomass nor the mea-
sured d15N values differed significantly (data not shown). The
d15Nc = measured d15N value of biomass or soil in unfertilized significantly higher mineral N uptake by plants growing on the
control treatment (only CO served as valid control treatment compost-amended plots (CO + F) was due to a significantly
as d15N did not differ between treatments without tracer appli- higher plant biomass production (Tab. 2).
cation),
Wardle et al. (1998) found greater tree-seedling growth, N
uptake, and enhanced efficiency of nutrient uptake in boreal
d15NNPK = d15N of (NH4)2SO4 10 atom% 15N excess forest soils when charcoal was added. The authors assumed
(= 29330.3‰). that adsorption of phenolics by the charcoal diminished
adverse effects on plant growth, both as allelopathic agents,
The amount of 15N remaining in soil or in plant biomass (Y) and through complexing N, thus reducing its availability to
was calculated according to Eq. 2. The subtraction of d15Nc in plants. In our case, soil analyses indicate that other nutrients
the denominator was neglected because it is small (approx. than N were more important to enhance plant growth leading
10 and 20 for soil and biomass, respectively) in comparison to N sequestration in biomass (Steiner et al., 2007). This
to d15NNPK. assumption is corroborated by the study of Alfaia et al. (2000)
who found only a 16% rice grain-yield increase due to
Nf d15 Nf Nf d15 Nc
Y 15
. (2) (NH4)2SO4 fertilization, but significant losses of fertilized N.
d NNPK
In the soil, the situation was rather different. After the second
The percentage of N taken up by biomass or remaining in the
harvest (HII), significantly more fertilizer N remained in the
soil was calculated according to Eq. 3:
soil amended with charcoal (15.6% of applied N) than on
Y plots without organic amendment (9.7%). The compost treat-
N% 100, (3)
N
NH4 2 SO4 ment showed intermediate values (12.6%) (Fig. 2). In the soil,
the increased retrieval of N rather than higher total soil N con-
where N(NH4)2SO4 = amount of tracer fertilized [27.5 kg ha–1 tents caused the significantly enhanced N recovery. Only
(NH4)2SO4 10 atom% 15N excess]. remaining crop residues could have caused the increase in
encountered 15N from HI to HII. However, the treatment ½CC
+ ½CO + F showed a much larger increase in soil 15N
2.3 Analyses of soil and plant samples encountered from HI to HII than the F treatment but had
slightly less crop-residue input (Tab. 2). Only the compost
Soil and plant samples were analyzed for their C and N con- treatment (CO + F) generated significantly more crop residue
tents by dry combustion with an automatic C/N-Analyzer (Ele- 15N than the control group but this additional residue return
mentar, Hanau, Germay). Total N isotope composition in soil did not significantly affect the soil 15N at HII.
and plants was determined using an Elemental Analyzer
(Carlo Erba NA 1500, Carlo Erba Reagenti, Rodano, Italy; for At least to some extent the accrued crop residues after HII
Dumas combustion) connected to an isotope-mass spectro- added to the soil’s N pool as shown by the shift in isotope
meter (FINNIGAN MAT delta E; Thermo Finnigan, San Jose values (data not shown) because soil sampling was done
CA) via a split interface. 7–14 d after the harvest. Belowground biomass was not
assessed and can contribute significantly to N cycling as the The significantly increased uptake of applied N by plants on
root biomass pool can be assumed to be at least half as large plots with additional compost and the significantly higher N
as the aboveground biomass pool (Lacerda et al., 2004; retention in the soil due to charcoal additions may be explained
Hattori et al., 2005). Lehmann and Zech (1998) found 30% of by either reduced N leaching (Lehmann et al., 2003) or reduced
sorghum roots in Kenya below 0.3 m. We sampled only the gaseous N losses (Yanai et al., 2007). Reduced N leaching may
upper 0.1 m, thus N could have been recycled from deeper be a result (1) of either improved retention of the applied NH
4 by
soil layers. electrostatic adsorption to exchange sites provided by the com-
Table 2: Biomass production, N uptake, and withdrawal (grains) at the first (HI) and second harvest (HII). Different letters in the same column
indicate significant differences (p < 0.05) between treatments (Fisher’s LSD test, n = 5).
HI HII HI HII
crop residues grains crop residues grains N residues N grains N residues N grains
Treatment [Mg dry matter ha–1] [kg ha–1]
F 1.38 b 0.28 c 0.50 c 0.14 c 11.3 c 4.7 c 4.9 b 2.3 c
CO 1.50 b 0.28 c 0.56 c 0.16 bc 19.8 b 5.8 c 7.5 b 3.2 bc
CO + F 2.69 a 0.96 a 1.17 a 0.80 a 29.8 a 15.5 a 13.1 a 12.6 a
CC + F 1.85 b 0.42 bc 0.72 bc 0.28 bc 17.3 bc 7.1 c 7.0 b 4.6 bc
½CC + ½CO + F 1.76 b 0.65 b 0.80 abc 0.33 bc 18.9 bc 11.8 ab 8.7 b 6.1 bc
CC + ½CO + F 2.08 ab 0.49 bc 0.97 ab 0.49 ab 19.7 b 8.1 bc 9.1 ab 8.5 ab
post or charcoal or (2) of immobilization of N by microbial bio- the activity of the nitrifying community and removes inhibiting
mass. Lehmann et al. (2003) made microbial immobilization phenols. We could not elucidate alterations in nitrification and its
responsible for decreases in foliar N contents and total N uptake possible consequences for leaching and denitrification,
as a response to charcoal additions due to their higher C : N although Birk (2005) found evidence that the organic amend-
ratio. However, their pot experiment used larger amounts of ments increased the presence of anaerobic bacteria which pos-
applied charcoal (67.6 and 135.2 Mg C ha–1) than our study. The sibly are denitrifiers. Dinkelmeyer et al. (2003) found a rapidly
C : N ratio in the soil studied here was found to be significantly decreasing total recovery (in plants and soil) of 15N (87% to 54%
higher in the charcoal treatments at both harvest times (Fig. 1) to 24% at 1, 3, and 12 months after N application, respectively),
in comparison to the control. Decomposition of a portion of but they assessed a complex and deep-rooting agroforestry
newly applied charcoal and concurrent N immobilization is most system to a soil depth of 5 m. They found a minimum of 13% N-
likely a transient phenomenon as charcoal is much more stable fertilizer efficiency when applied to peach palm (Bactris gasi-
than other organic additions (Baldock and Smernik, 2002). In paes) and a maximum of 38% if applied to cupuassu (Theo-
the studied permeable soils under high-rainfall conditions, broma grandiflorum). Alfaia et al. (2000) assessed N utilization
temporary immobilization of mobile nutrients might be desirable. of a rice crop grown in central Amazona and found a N-fertilizer
The results of the 15N experiments by Burger and Jackson efficiency of only 7.8%, 10.0%, and 1% in shoot, grain, and root
(2003) suggest a very dynamic role of microbially bound N and biomass, respectively. We found a maximum recovery in plant
highlight the importance of N immobilization that is taking place biomass of 15% and total recovery of 22% 3 months after N
simultaneously with inorganic-N production by mineralization. application at HI. Already after 4 d, Renck and Lehmann (2004)
They concluded that greater C availability stimulates microbial found applied 15N in the soil solution to a depth of 0.6 m and to a
activity resulting in greater N demand, promoting immobilization depth of 5 m after 1 week at the same study site. They found that
and recycling of NO3 . The resilience of soil C in charcoal- the largest part of applied 15N in the top soil was leached as
amended plots shows the refractory nature of charcoal (Kuhl- organic N. The total fluxes of organic N were similar to those of
busch and Crutzen, 1995). While the stability of charcoal leads NO3 in the topsoil. According to Lehmann et al. (2002), the NH 4
to low C losses, nutrient release by mineralization is most likely adsorbability of charcoal is largely dependent on soluble OM, as
lower than from other organic materials. As charcoal is expected an addition of DOC from a manure extract increased NH 4
to be an extremely recalcitrant form of OM, it is unknown to what adsorption. Therefore charcoal might have reduced leaching of
extent charcoal C favors N immobilization. In previous studies, organic N in addition to the inorganic forms. The organic amend-
the same plots showed significantly increased plant growth and ments might likewise have altered denitrification but leaching is
potential for microbial-population growth in mineral-fertilized most likely the predominant N loss in the studied soil and the
soils amended with charcoal and in Terra Preta, but lower micro- relative proportion could not be clarified in this study.
bial respiration in the absence of an easily degradable C source
(glucose) compared to soils without charcoal (Steiner et al., The charcoal’s low biodegradability (Kuhlbusch and Crutzen,
2004a, 2007). It has been shown that charcoal amendments 1995), low nutrient content (Ogawa, 1994; Antal and Grønli,
can significantly enhance nitrification in pine-forest soils 2003), and high porosity and specific surface area (Braida
(DeLuca et al., 2006). The authors suggest that charcoal alters et al., 2003) makes charcoal a rather exceptional SOM con-
stituent. Terra Preta research has shown that oxidation on DeLuca, T. H., Kenzie, M. D. M., Gundale, M. J., Holben, W. E.
the edges of the aromatic backbone and adsorption of other (2006): Wildfire-produced charcoal directly influences nitrogen
OM to charcoal is responsible for the increased CEC, though cycling in Ponderosa pine forests. Soil Sci. Soc. Am. J. 70,
the relative importance of these two processes remains 448–453.
unclear (Liang et al., 2006). Dinkelmeyer, H., Lehmann, J., Renck, A., Trujillo, L. Jr., J. P. d. S.,
Gebauer, G., Kaiser, K. (2003): Nitrogen uptake from 15N-enriched
fertilizer by four tree crops in an Amazonian agroforest. Agroforest.
4 Conclusion Syst. 57, 213–224.
Duxbury, J. M., Smith, M. S., Doran, J. W., Jordan, C., Szott, L.,
We conclude that both the higher retention of N in the soil Vance, E. (1989): Soil Organic Matter as a Source and a Sink of
and the increased uptake by biomass are responsible for the Plant Nutrients, in Coleman, D. C., Oades, J. M., Uehara, G.
significantly enhanced N cycling in plots that received char- (eds.): Dynamics of Soil Organic Matter in Tropical Ecosystems.
coal. Soil charcoal amendments improve the efficiency of University of Hawaii Press, Honolulu, pp. 33–67.
mineral N fertilizer. FAO (1990): Soil map of the world, revised legend. FAO, Rome, Italy.
Fearnside, P. M. (1997): Greenhouse gases from deforestation in
Brazilian Amazonia: Net committed emissions. Climatic Change.
Acknowledgments 35, 321–360.
The research was conducted within SHIFT ENV 45, a Ger- Fearnside, P. M., Lima, P. M., Graça, A., Rodrigues, F. J. A. (2001):
Burning of Amazonian rainforest: burning efficiency and charcoal
man–Brazilian cooperation and financed by BMBF, Germany
formation in forest cleared for cattle pasture near Manaus, Brazil.
and CNPq, Brazil (BMBF No. 0339641 5A, CNPq 690003/ Forest Ecol. Manage. 146, 115–128.
986). A financial contribution was given by the doctoral scho-
larship program of the Austrian Academy of Sciences. We Fernandes, E. C. M., Motavalli, P. P., Castilla, C., Mukurumbira, L.
(1997): Management control of soil organic matter dynamics in
are grateful for the fieldworkers’ help particularly Luciana Fer-
tropical land-use systems. Geoderma 79, 49–67.
reira da Silva and Franzisco Aragão Simão and the laborato-
ry technician Marcia Pereira de Almeida. Jago Birk helped Giardina, C. P., Sanford, R. L., Dockersmith, I. C., Jaramillo, V. J.
during an internship on the field and in the laboratory. (2000): The effects of slash burning on ecosystem nutrients during
the land preparation phase of shifting cultivation. Plant Soil 220,
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Abstract
Leaching losses of N are a major limitation of crop production on permeable soils and under
heavy rainfalls as in the humid tropics. We established a field trial in the central Amazon (near
Manaus, Brazil) in order to study the influence of charcoal and compost on the retention of N.
Fifteen months after organic-matter admixing (0–0.1 m soil depth), we added 15N-labeled
(NH4)2SO4 (27.5 kg N ha–1 at 10 atom% excess). The tracer was measured in top soil (0–0.1 m)
and plant samples taken at two successive sorghum (Sorghum bicolor L. Moench) harvests.
The N recovery in biomass was significantly higher when the soil contained compost (14.7% of
applied N) in comparison to only mineral-fertilized plots (5.7%) due to significantly higher crop
production during the first growth period. After the second harvest, the retention in soil was sig-
nificantly higher in the charcoal-amended plots (15.6%) in comparison to only mineral-fertilized
plots (9.7%) due to higher retention in soil. The total N recovery in soil, crop residues, and grains
was significantly (p < 0.05) higher on compost (16.5%), charcoal (18.1%), and charcoal-plus-
compost treatments (17.4%) in comparison to only mineral-fertilized plots (10.9%). Organic
amendments increased the retention of applied fertilizer N. One process in this retention was
found to be the recycling of N taken up by the crop. The relevance of immobilization, reduced N
leaching, and gaseous losses as well as other potential processes for increasing N retention
should be unraveled in future studies.
Key words: biochar Brazil / carbon / nitrogen cycling / slash-and-burn / soil organic matter / Terra Preta
The sustained fertility of charcoal-containing Terra Preta and The charcoal derived from secondary forest wood and was
the frequent use of charcoal as a soil conditioner (Steiner considered rather as soil conditioner than fertilizer due to the
et al., 2004b) in Brazil provided the incentive to study the charcoal’s low nutrient contents (Tab. 1). It was manually
effects of charcoal application on N cycling. Charcoal acted crushed to particle sizes <2 mm. The applied 11 Mg ha–1
as an adsorber which reduced N leaching in previous pot corresponded to the amount of charcoal-C which could be
experiments (Lehmann et al., 2002, 2003), and charcoal produced by a single slash-and-char event of a tropical
additions proved to sustain fertility if an additional nutrient secondary forest on Xanthic Ferralsols in central Amazonia
source is given in a field trial (Steiner et al., 2007). Charcoal (Lehmann et al., 2002). The amount of C added with charcoal
plus fertilizer improved plant growth and doubled grain pro- was chosen as a reference value for adding the compost.
duction in comparison to the fertilizer without charcoal. Plant Compost was prepared from biomass of a secondary forest,
biomass production sharply decreased within 1 y when only fruit residues, manure, and kitchen waste. On February 3,
mineral fertilizer was applied, but could be maintained for a 2001, organic materials were mixed with hand hoes into the
longer period of time when OM was added. The authors pro- top soil (0–0.1 m) of the plots, and the first mineral fertilization
posed that charcoal can improve soil chemical, biological, was done on March 19, 2001 [30 N kg ha–1 as (NH4)2SO4,
and physical properties, but could not completely discern the 35 kg P ha–1 as simple superphosphate, 50 kg K ha–1 as KCl,
mechanisms of fertility enhancement (Steiner et al., 2007). and 2100 kg lime ha–1]. The fields were cropped twice (rice
Oryza sativa L. and sorghum Sorghum bicolor L. Moench)
Stable isotopes such as 15N can serve as valuable tracers to prior the second fertilization on April 16 (see Tab. 1 for treat-
study plant resource acquisition and as a means to understand ment description). All crop residues remained on the field,
how plants interact with their abiotic and biotic environments and only grains were removed. Sorghum was planted again
(Dawson et al., 2002). Therefore, our objective was to compare on April 18, 2002 in a density of 25 plants m–2 producing two
the effect of organic amendments such as charcoal and com- harvests by ratooning (July 21 and October 16, 2002). Only
post on retention of 15N-labeled mineral fertilizer in a highly these two harvests are subject of the present paper and
weathered Ferralsol under humid tropical field conditions. designated as 1st (HI) and 2nd (HII) harvest.
applied at a rate of 55 kg N ha–1 in April 2002 (second fertili- 2.4 Statistical analyses
zation). Additionally, 40 kg P ha–1, 50 kg K ha–1, and 430 kg
ha–1 of lime was applied. Soil and plant samples were taken Treatment effects were analyzed by one-way analysis of var-
at each harvest and analyzed for d15N. Only the top 0.1 m of iance (ANOVA). Significant treatment effects were detected
soil was sampled, this was also the depth down to which the using the Fisher’s LSD (last significant difference) test. Statis-
organic amendments were mixed. Two soil samples were tical analyses and figures were performed using SPSS 12.0
taken per plot to form one composite sample. Soils were air- (SPSS Inc.) and SigmaPlot 7.0.
dried and ground before isotope analysis. Representative
plant samples were taken from the entire crop by using the
center 1.4 × 1.4 m (49 plants) of each plot. Plant samples
3 Results and discussion
were dried at 70°C for 48 h and ground. While the soil C contents were significantly increased by the
organic amendments (CO and CC), the N values were only
The remaining fertilizer N in soil or plant biomass was calcu- significantly enhanced in comparison to the F plots if CO was
lated after Eq. 1 (Boutton, 1996). applied (Fig. 1). After the second harvest (HII), the N and C
contents on solely compost-amended plots (CO) did not differ
Nf d15 Nf Nf d15 Nc Y d15 NNPK , (1) from those receiving only mineral fertilizer. The OM-amended
and N-fertilized plots had significantly higher C and N con-
tents than the F plots. All organic amendments significantly
Nf = nitrogen content of biomass or soil in N-fertilized treat- increased the C : N ratio after the first harvest. This difference
ment, was even more distinct after the second harvest but only on
charcoal-containing plots (Fig. 1).
d15Nf = measured d15N value of biomass or soil in N-fertilized
treatment, Neither the N concentrations in the biomass nor the mea-
sured d15N values differed significantly (data not shown). The
d15Nc = measured d15N value of biomass or soil in unfertilized significantly higher mineral N uptake by plants growing on the
control treatment (only CO served as valid control treatment compost-amended plots (CO + F) was due to a significantly
as d15N did not differ between treatments without tracer appli- higher plant biomass production (Tab. 2).
cation),
Wardle et al. (1998) found greater tree-seedling growth, N
uptake, and enhanced efficiency of nutrient uptake in boreal
d15NNPK = d15N of (NH4)2SO4 10 atom% 15N excess forest soils when charcoal was added. The authors assumed
(= 29330.3‰). that adsorption of phenolics by the charcoal diminished
adverse effects on plant growth, both as allelopathic agents,
The amount of 15N remaining in soil or in plant biomass (Y) and through complexing N, thus reducing its availability to
was calculated according to Eq. 2. The subtraction of d15Nc in plants. In our case, soil analyses indicate that other nutrients
the denominator was neglected because it is small (approx. than N were more important to enhance plant growth leading
10 and 20 for soil and biomass, respectively) in comparison to N sequestration in biomass (Steiner et al., 2007). This
to d15NNPK. assumption is corroborated by the study of Alfaia et al. (2000)
who found only a 16% rice grain-yield increase due to
Nf d15 Nf Nf d15 Nc
Y 15
. (2) (NH4)2SO4 fertilization, but significant losses of fertilized N.
d NNPK
In the soil, the situation was rather different. After the second
The percentage of N taken up by biomass or remaining in the
harvest (HII), significantly more fertilizer N remained in the
soil was calculated according to Eq. 3:
soil amended with charcoal (15.6% of applied N) than on
Y plots without organic amendment (9.7%). The compost treat-
N% 100, (3)
N
NH4 2 SO4 ment showed intermediate values (12.6%) (Fig. 2). In the soil,
the increased retrieval of N rather than higher total soil N con-
where N(NH4)2SO4 = amount of tracer fertilized [27.5 kg ha–1 tents caused the significantly enhanced N recovery. Only
(NH4)2SO4 10 atom% 15N excess]. remaining crop residues could have caused the increase in
encountered 15N from HI to HII. However, the treatment ½CC
+ ½CO + F showed a much larger increase in soil 15N
2.3 Analyses of soil and plant samples encountered from HI to HII than the F treatment but had
slightly less crop-residue input (Tab. 2). Only the compost
Soil and plant samples were analyzed for their C and N con- treatment (CO + F) generated significantly more crop residue
tents by dry combustion with an automatic C/N-Analyzer (Ele- 15N than the control group but this additional residue return
mentar, Hanau, Germay). Total N isotope composition in soil did not significantly affect the soil 15N at HII.
and plants was determined using an Elemental Analyzer
(Carlo Erba NA 1500, Carlo Erba Reagenti, Rodano, Italy; for At least to some extent the accrued crop residues after HII
Dumas combustion) connected to an isotope-mass spectro- added to the soil’s N pool as shown by the shift in isotope
meter (FINNIGAN MAT delta E; Thermo Finnigan, San Jose values (data not shown) because soil sampling was done
CA) via a split interface. 7–14 d after the harvest. Belowground biomass was not
assessed and can contribute significantly to N cycling as the The significantly increased uptake of applied N by plants on
root biomass pool can be assumed to be at least half as large plots with additional compost and the significantly higher N
as the aboveground biomass pool (Lacerda et al., 2004; retention in the soil due to charcoal additions may be explained
Hattori et al., 2005). Lehmann and Zech (1998) found 30% of by either reduced N leaching (Lehmann et al., 2003) or reduced
sorghum roots in Kenya below 0.3 m. We sampled only the gaseous N losses (Yanai et al., 2007). Reduced N leaching may
upper 0.1 m, thus N could have been recycled from deeper be a result (1) of either improved retention of the applied NH
4 by
soil layers. electrostatic adsorption to exchange sites provided by the com-
Table 2: Biomass production, N uptake, and withdrawal (grains) at the first (HI) and second harvest (HII). Different letters in the same column
indicate significant differences (p < 0.05) between treatments (Fisher’s LSD test, n = 5).
HI HII HI HII
crop residues grains crop residues grains N residues N grains N residues N grains
Treatment [Mg dry matter ha–1] [kg ha–1]
F 1.38 b 0.28 c 0.50 c 0.14 c 11.3 c 4.7 c 4.9 b 2.3 c
CO 1.50 b 0.28 c 0.56 c 0.16 bc 19.8 b 5.8 c 7.5 b 3.2 bc
CO + F 2.69 a 0.96 a 1.17 a 0.80 a 29.8 a 15.5 a 13.1 a 12.6 a
CC + F 1.85 b 0.42 bc 0.72 bc 0.28 bc 17.3 bc 7.1 c 7.0 b 4.6 bc
½CC + ½CO + F 1.76 b 0.65 b 0.80 abc 0.33 bc 18.9 bc 11.8 ab 8.7 b 6.1 bc
CC + ½CO + F 2.08 ab 0.49 bc 0.97 ab 0.49 ab 19.7 b 8.1 bc 9.1 ab 8.5 ab
post or charcoal or (2) of immobilization of N by microbial bio- the activity of the nitrifying community and removes inhibiting
mass. Lehmann et al. (2003) made microbial immobilization phenols. We could not elucidate alterations in nitrification and its
responsible for decreases in foliar N contents and total N uptake possible consequences for leaching and denitrification,
as a response to charcoal additions due to their higher C : N although Birk (2005) found evidence that the organic amend-
ratio. However, their pot experiment used larger amounts of ments increased the presence of anaerobic bacteria which pos-
applied charcoal (67.6 and 135.2 Mg C ha–1) than our study. The sibly are denitrifiers. Dinkelmeyer et al. (2003) found a rapidly
C : N ratio in the soil studied here was found to be significantly decreasing total recovery (in plants and soil) of 15N (87% to 54%
higher in the charcoal treatments at both harvest times (Fig. 1) to 24% at 1, 3, and 12 months after N application, respectively),
in comparison to the control. Decomposition of a portion of but they assessed a complex and deep-rooting agroforestry
newly applied charcoal and concurrent N immobilization is most system to a soil depth of 5 m. They found a minimum of 13% N-
likely a transient phenomenon as charcoal is much more stable fertilizer efficiency when applied to peach palm (Bactris gasi-
than other organic additions (Baldock and Smernik, 2002). In paes) and a maximum of 38% if applied to cupuassu (Theo-
the studied permeable soils under high-rainfall conditions, broma grandiflorum). Alfaia et al. (2000) assessed N utilization
temporary immobilization of mobile nutrients might be desirable. of a rice crop grown in central Amazona and found a N-fertilizer
The results of the 15N experiments by Burger and Jackson efficiency of only 7.8%, 10.0%, and 1% in shoot, grain, and root
(2003) suggest a very dynamic role of microbially bound N and biomass, respectively. We found a maximum recovery in plant
highlight the importance of N immobilization that is taking place biomass of 15% and total recovery of 22% 3 months after N
simultaneously with inorganic-N production by mineralization. application at HI. Already after 4 d, Renck and Lehmann (2004)
They concluded that greater C availability stimulates microbial found applied 15N in the soil solution to a depth of 0.6 m and to a
activity resulting in greater N demand, promoting immobilization depth of 5 m after 1 week at the same study site. They found that
and recycling of NO3 . The resilience of soil C in charcoal- the largest part of applied 15N in the top soil was leached as
amended plots shows the refractory nature of charcoal (Kuhl- organic N. The total fluxes of organic N were similar to those of
busch and Crutzen, 1995). While the stability of charcoal leads NO3 in the topsoil. According to Lehmann et al. (2002), the NH 4
to low C losses, nutrient release by mineralization is most likely adsorbability of charcoal is largely dependent on soluble OM, as
lower than from other organic materials. As charcoal is expected an addition of DOC from a manure extract increased NH 4
to be an extremely recalcitrant form of OM, it is unknown to what adsorption. Therefore charcoal might have reduced leaching of
extent charcoal C favors N immobilization. In previous studies, organic N in addition to the inorganic forms. The organic amend-
the same plots showed significantly increased plant growth and ments might likewise have altered denitrification but leaching is
potential for microbial-population growth in mineral-fertilized most likely the predominant N loss in the studied soil and the
soils amended with charcoal and in Terra Preta, but lower micro- relative proportion could not be clarified in this study.
bial respiration in the absence of an easily degradable C source
(glucose) compared to soils without charcoal (Steiner et al., The charcoal’s low biodegradability (Kuhlbusch and Crutzen,
2004a, 2007). It has been shown that charcoal amendments 1995), low nutrient content (Ogawa, 1994; Antal and Grønli,
can significantly enhance nitrification in pine-forest soils 2003), and high porosity and specific surface area (Braida
(DeLuca et al., 2006). The authors suggest that charcoal alters et al., 2003) makes charcoal a rather exceptional SOM con-
stituent. Terra Preta research has shown that oxidation on DeLuca, T. H., Kenzie, M. D. M., Gundale, M. J., Holben, W. E.
the edges of the aromatic backbone and adsorption of other (2006): Wildfire-produced charcoal directly influences nitrogen
OM to charcoal is responsible for the increased CEC, though cycling in Ponderosa pine forests. Soil Sci. Soc. Am. J. 70,
the relative importance of these two processes remains 448–453.
unclear (Liang et al., 2006). Dinkelmeyer, H., Lehmann, J., Renck, A., Trujillo, L. Jr., J. P. d. S.,
Gebauer, G., Kaiser, K. (2003): Nitrogen uptake from 15N-enriched
fertilizer by four tree crops in an Amazonian agroforest. Agroforest.
4 Conclusion Syst. 57, 213–224.
Duxbury, J. M., Smith, M. S., Doran, J. W., Jordan, C., Szott, L.,
We conclude that both the higher retention of N in the soil Vance, E. (1989): Soil Organic Matter as a Source and a Sink of
and the increased uptake by biomass are responsible for the Plant Nutrients, in Coleman, D. C., Oades, J. M., Uehara, G.
significantly enhanced N cycling in plots that received char- (eds.): Dynamics of Soil Organic Matter in Tropical Ecosystems.
coal. Soil charcoal amendments improve the efficiency of University of Hawaii Press, Honolulu, pp. 33–67.
mineral N fertilizer. FAO (1990): Soil map of the world, revised legend. FAO, Rome, Italy.
Fearnside, P. M. (1997): Greenhouse gases from deforestation in
Brazilian Amazonia: Net committed emissions. Climatic Change.
Acknowledgments 35, 321–360.
The research was conducted within SHIFT ENV 45, a Ger- Fearnside, P. M., Lima, P. M., Graça, A., Rodrigues, F. J. A. (2001):
Burning of Amazonian rainforest: burning efficiency and charcoal
man–Brazilian cooperation and financed by BMBF, Germany
formation in forest cleared for cattle pasture near Manaus, Brazil.
and CNPq, Brazil (BMBF No. 0339641 5A, CNPq 690003/ Forest Ecol. Manage. 146, 115–128.
986). A financial contribution was given by the doctoral scho-
larship program of the Austrian Academy of Sciences. We Fernandes, E. C. M., Motavalli, P. P., Castilla, C., Mukurumbira, L.
(1997): Management control of soil organic matter dynamics in
are grateful for the fieldworkers’ help particularly Luciana Fer-
tropical land-use systems. Geoderma 79, 49–67.
reira da Silva and Franzisco Aragão Simão and the laborato-
ry technician Marcia Pereira de Almeida. Jago Birk helped Giardina, C. P., Sanford, R. L., Dockersmith, I. C., Jaramillo, V. J.
during an internship on the field and in the laboratory. (2000): The effects of slash burning on ecosystem nutrients during
the land preparation phase of shifting cultivation. Plant Soil 220,
247–260.
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Makoto Ogawa
Introduction
In Asian countries, the highly intensive agriculture has been popular since ancient days
because of high population density, limited arable field and rice plant cultivation. Therefore,
various traditional cultivation techniques had developed in order to raise the productivity of
crops. Any kinds of wastes, the excretions of human and live stocks, straw, leaf litter,
grass、sewages and rice husk charcoal has been used as for the fertilizers and soil
amendments not only in agriculture but also gardening or greening. Particularly wood ash
containing some cinders was used as an important material for soil amendment and mineral
supply.
In Japan where the domestic supply of energy sources has been limited, the forest
resources, fire wood and charcoal were a most important energy source until the beginning of
20th century. Charcoal production and consumption increased depending on the increase of
population and reached to the maximum, 2.7 million ton per year in 1947. It may be estimated
that the wood, mainly broad leaved trees, of about 10 million ton was carbonized by the
traditional kiln at that time (1).
However, according to the rapid increase of the imported fossil fuels in 1960s, so called
“Fuel Revolution” progressed, and the productivity of charcoal decreased to the minimum,
about 30 thousand ton per year in 1980s. The abrupt changes in the people’s daily life and the
relations between human and forest caused the decrease of Matsutake mushroom,
mycorrhizal fungus and the outbreak of pine wilting disease (2).
In 1970s, under such a circumstance, late Dr. Kishimoto S. and Sugiura G. who were the
experts of charcoal and wood vinegar production began the movement to make revive charcoal
and to encourage the new use. In 1980 they published a book “ Introduction to charcoal
making on Sunday ” (3) and distributed the knowledge of popular charcoal making and use.
They contributed largely toward the present prosperity of charcoal business in Japan and
Asia. The author, Ogawa M. and his colleagues started the studies on the utilization of
charcoal in agriculture and forestry on their requests in 1980 and reported the effects of bark
charcoal on soy bean and pine tree in 1983 (4) (5).
Being encouraged by their activities and the extension of organic farming in Japan, the
application and studies of charcoal in agriculture began actively in 1980s. In 1986, “Technical
Research Association for Multiuse of Carbonized Materials” (TRA) was established by the
financial support of Forest Agency, and the studies of new charcoal use launched being
participated with 13 private companies for 3 years. The studies on the effects of charcoal and
wood vinegar were conducted covering the various fields; the improvement of carbonization
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By the report, the effects of charcoal and wood vinegar were recognized in public and
authorized as a specific material of soil amendment by MAFF (Ministry of Agriculture,
Forestry and Fishery) in1990. Contrary to the government expectation to raise the charcoal
production in rural area, the cheaper charcoals which are imported from Southeast Asia being
produced from coconut and oil palm shells has reached to the same amount with those in
domestic. In this paper, only the publications written by Japanese are introduced, because it
seems to be unavailable in other countries.
The oldest description on charcoal use in agriculture is found in a text book, “ Nogyo Zensho
( Encyclopedia of Agriculture )” written by Yasusada Miyazaki in 1697 (7). He described in it;
“After roasting every wastes, the dense excretions should be mixed with it and stocked for a
while. This manure is efficient for the yields of any crops. It is called the fire manure”.
Probably the similar knowledge had been popular in China and Korea since ancient time.
In Asian countries, the rice husk charcoal which can be carbonized by simple method in field
soon after harvesting has been one of the most common materials for soil amendment. It
seems that the rice husk charcoal has been used for several thousand years since the
beginning of rice cultivation in Asia, because rice husk with high content of silica is hardly
decomposed and unavailable for the manure.
The custom to use rice husk charcoal mixed with the excretions had spread among farmers
particularly in wheat cultivation until about 60 years ago. It seems to be reasonable, because
the charcoal can absorb and keep chemical nutrients and deodorize the stench. However, this
method was too popular to investigate for scientists, and so the roles of charcoal in agriculture
had been neglected for long time. After the information on wood charcoal use circulated
in1980’s, the roles of rice husk charcoal have been noticed in the research field of agriculture.
Recently Ezawa T. et al. (8) reported that rice husk and its charcoal enhanced A (arbuscular)
mycorhiza formation of some crop plants and improved the soil physical properties when each
of them was added into top soil. Ishii T. et al. (9) also reported the same effects on the A
mycorrhiza formation of citrus seedlings. Komaki Y. et al. (10) suggested that a small amount
of rice husk charcoal was effective on the growth of Catharanthus roseus, but the browning of
leaves appeared with the excessive application because of high concentration of potassium
and higher pH than wood charcoal. Takagi K. et al. (11) proposed a practical method to reduce
the outflow of pesticides and herbicides from paddy field utilizing the absorbing ability of rice
husk charcoal. Also he tried to fix the bacteria with high decomposing ability of pesticide into
rice husk charcoal and succeeded to reduce the outflow from golf course (12).
At present, the carbonizing method has developed from the traditional method to the
sophisticated facility equipped at the rice mill. Dried rice husk can be carbonized
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automatically and continuously in the self-burning kiln and the extra heat is utilized for small
scale power generation (13). Recently the facility and system have been exported to South
East Asia by the company. Probably it is possible to apply to the wheat and barley husks and
other crop plant residues.
In Asian countries, the studies of charcoal use in agriculture have been mostly carried out by
JICA experts. In Indonesia, Igarashi T. started the experiment to produce the rice husk
charcoal with simple method and to cultivate soy bean and maize with the charcoal in 1989
(14). Igarashi T. et al. (15) applied the charcoal together with magnesium phosphate and lime
respectively and tried to rotate soy bean with maize. The charcoal application enhanced root
nodule formation, plant growth and the yields significantly. The effect was sustained also in
the second crop of maize without any supply of fertilizers, and the after effect was observed up
to 10th rotation. In particular, the growth and yield of maize treated with the charcoal were
more than that in the control plot cultivated only by chemical fertilizer. He also tried to apply
the charcoal in several areas with different soil condition and reported that the effect seemed
to be different from the soil properties and the kind of crops (16). Since the publication of
experiment results, charcoal use is advancing in Indonesia.
In Thailand, Oka H. et al. (17) studied the effects of rice husk charcoal on the growth, yield
and nitrogen fixation rates of soy bean which was planted in the infertile sandy soil. He
reported that the amount of upper ground biomass, root, soy bean yield and the rate of
nitrogen fixation in soil increased significantly. In field, the application of 10 ton per hectare
was most efficient, and the effect appeared evidently in the second crop of sorghum and the
third of soy bean. The soil physical properties, porosity, water holding capacity, pH and CEC
were also improved, although the values were different depending on soil type.
In Philippine, Noguti A. et al. (18) confirmed the effect of rice husk charcoal on the growth of
beans in an infertile acidic red soil. In this experiment the rice husk charcoal of 2.5 t / ha and
lime of 1.5 t/ha were applied and mixed with top soil 15 cm in depth, chemical fertilizer was
applied and the root nodule bacteria inoculated. The number of root nodule and nitrogen
fixing rates increased in the plot with lime, but it was more stimulated evidently by the
addition of charcoal. The inoculation of root nodule bacteria and the application of rice husk
charcoal induced the same effect with single use of lime. It seems to be meaningful
economically in Philippine where the use of lime is rather costly for farmers.
In 1983, Ogawa M. et al. (4, 5) reported that the bark charcoal powders containing a small
amount of chemical fertilizers were efficient for the mycorrhiza formation of pine tree and the
A mycorrhiza and root nodule formations of soy bean plant. In the experiment of soy bean
plant (19), the bark charcoal of broad leaved tree was mixed with 1 % (W / W) of the inorganic
fertilizer (N: P: K (8: 8: 8)), urea, super lime phosphate, ammonium sulfate and oil cake
powder respectively. These charcoal fertilizers were stocked for one week and scattered over
soil surface at 500 g / m2 and 1500g / m2 each before plowing. Soy bean seedlings without root
nodules were planted in each plot. The plots in which applied the inorganic chemical fertilizer,
100 g / m2 and 200 g / m2 and the control plot without any treatments were set to compare the
efficiency.
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Soy bean yields which were harvested from the plots with charcoal fertilizers of 500 g / m2
were mostly equal to those from the plots with 100 and 200 g of chemical fertilizer. By this
method the amount of chemicals could be saved remarkably to 1/20. Root nodule formation
was stimulated by charcoal fertilizers, but it was suppressed by the ones with ammonium
sulfate and synthetic chemical fertilizer. A mycorrhiza infection rates and the spore numbers
increased in the plots treated with charcoal fertilizers. It seems that the better growth of soy
bean plants resulted from the enhanced root growth and propagation of symbiotic
microorganisms being activated by the charcoal0..
The soil microbial flora in each plot changed with the application of charcoal fertilizers.
Charcoal fertilizers with higher pH than 8 inhibited the propagation of soil fungi, but
enhanced that of bacteria and Actinomycetes soon after the treatment and then returned to
the normal state gradually. It was prospected that the emission of carbon dioxide increased
temporarily being caused by the high microbial activity. At the same time, the free living
nitrogen fixing bacteria could be isolated on the nitrogen free medium. From the inoculation
test of the charcoal which was sterilized and buried in soil for a week, it was certain that the
charcoal became the habitat for root nodule bacteria (19).
The charcoal which was carbonized under high temperature is usually alkaline and porous
substance, and there is no substrate for saprophytic microorganisms. When the charcoal was
added into soil, at first the plant root grows toward the charcoal with enough water and air.
Next some microorganisms which can endure under high alkalinity can propagate in or
around charcoal. It seems that the charcoal provides a better habitat for the root and
symbiotic microorganisms.
These research results were confirmed also in the TRA. Wood charcoal was efficient to
improve the soil properties, but the mixtures with chemical fertilizers, zeolite, wood vinegar
and organic fertilizer exhibited the better effects than charcoal itself on tea plant, citrus and
vegetables (20), rice plant and apple tree (21) and some leguminous plants and grass for
greening (22).
It was found that root nodule bacteria could be immobilized with high frequency in the white
and hard charcoal with fine pores. So, Takagi S. (23) proposed the method to make the
inoculum of root nodule bacteria of leguminous plants utilizing the charcoal. On the other
hand, A mycorrhizal fungi showed the better growth on black charcoal which was carbonized
at 400-500 degree Celsius. The spore of Gigaspora margarita was formed in black volcanic soil
with high carbon content (24). The application of wood charcoal to the plant associated with
Frankia was effective also for the actinorhiza formation (25). In general, it is certain from
these results that the white charcoal with the fine pore and high pH is suitable for the
immobilization of bacteria and the black one for that of fungi. After the study of TRA Oohira
T. et al. (26) reported that the oak charcoal with finer pores than that of pine was suitable for
the immobilization of bacteria and Actinomycetes than that of pine. Meanwhile, the
immobilizing ability of pine charcoal could be improved by mixing of acetic acid. Matsubara Y.
et al. (27) reported that coconut shell charcoal and the inoculation of A mycorrhizal fungi were
effective to suppress the infection of soil born pathogen Fusarium spp..
The research results of charcoal use in various fields were distributed not only in Japan but
also in Asian countries mainly by Ogawa M. (28) (29) (30).
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In Japan, the compost making from litter and excretions and its use has been very
common for long time. Ash or carbonized material was an essential material to accelerate the
decomposition stimulating the bacterial activity and to neutralize the acidity. It is also well
known that the charcoal absorbs smell and liquid.
In 1980s, a private company invented the method to produce charcoal compost which was
made from fresh chicken dung and palm shell charcoal tip (31). In the process of compost
making, the more the charcoal is used, the faster the decomposition progresses with
exothermic reaction. Under aerobic condition Bacillus group became dominant and produces
antibiotics. Kobayasi (32) reported that these antibiotics inhibited the growth of some soil
born pathogens, Pythium, Rhizoctonia, Phytophtra and Fusarium and were effective to
suppress root diseases of various plants. At present the charcoal compost (Haipuro) has been
sold as a biological fungicide by the company. Following this instance, various kinds of organic
composts have been produced from other livestock excretions and charcoal and sold in market.
It had been also well known that the liquid flowing out of charcoal kiln was useful. Actually it
had been used in forestry nursery bed as a pesticide and at road side as a herbicide. Kishimoto
S. et al. (33) published a text book in which they recommended the utilization of wood vinegar
in agriculture, forestry, animal husbandry and food processing describing the methods for the
purification, distillation and filtration.
Wood vinegar is a byproduct which is obtained from the carbonization process cooling the
smoke by air or water. This liquid contains the volatile substances emitted with pyrolysis;
water soluble fraction is wood vinegar and the oily one is wood tar. The chemical composition
is different depending on raw materials. Major components of broad leaved trees are 81 %
water, acetic acid 8-10 %, methanol 2.44 %, acetone 0.56 % and soluble tar 7 %, and that of
conifers are rich in water, acetic acid 3.5 % and the others concentrations are lower than that
of broad leaved trees (34). The chemical components of wood vinegar containing many organic
substances are unstable, so it has been sold as the material complex.
It has been recognized since 1960s that the wood vinegars extracted from broad leaved trees
are more efficient for the growth and rooting of various plants than that of conifers. The
effects were confirmed also in the study of TRA (35) (36) (37). The concentrated liquid of wood
vinegar with strong acidity shows the effects to kill microorganisms, plants and some larvae,
but the diluted one to stimulate rooting, plant growth and microbial propagation. There are
many reports of the application in field practice and generally the effects have been well
known by users, but there are a few available scientific reports on the mechanisms because of
the chemical property.
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In 1980, Ogawa et al. (38) tried to apply the bark charcoal powders with a small amount of
chemical fertilizers and succeeded to promote the growth of pine, Pinus thunbergii and
cultivate the mycorrhizal fungi, Rhizopogon rubescens which is a dominant mycorrhizal
species in the young stand with infertile basic sand
Some chemical fertilizers, urea, ammonium sulfate, super lime phosphate and synthetic
chemical fertilizer, were added to bark charcoal powder with 0.1-1.0% (W / W) respectively.
These materials were buried into the trenches 30 cm in depth and width after cutting the roots
and covered by sand. The regenerated fresh roots grew inside the charcoal layers vigorously
after 3 months and the mushrooms appeared abundantly along the trenches 9 months later.
After a year, the amounts of pine root and mycorrhiza increased remarkably in the charcoal
layers. In addition, the growth of shoots and the color of needles became better than before
treatment. These apparent effects probably resulted from the regeneration of root and the
formation of mycorrhiza. It might be caused from the enhanced nutrient uptake and the water
absorption through mycorrhiza. The water content in the charcoal was eminently higher and
it was kept 40 % even in mid summer comparing with 5 % outside the charcoal layer (39).
After releasing the experiment result the similar phenomena were confirmed by many
researchers in local forest experiment stations, because it is an edible mushroom in Japan.
For example Hirasa T. (40) devised the growing method of seedling with the mycorrhiza and
the cultivation method in field.
The same method has been widely accepted by professional gardeners and applied to various
kinds of tree species to make revive the famous trees in shrine, temple and park. Usually the
charcoal powder, maximum 1 cm in diameter, has been buried into trench or hole together
with a small amount of phosphate fertilizer and the spores of suitable mycorrhizal fungi to
host plant. Sometimes the root system was exposed removing top soil and covered by charcoal
powder as well. Also in nursery, the charcoal fertilizer is mixed with pot soil to improve soil
properties and inoculate the mycorrhizal fungi (41).
Both pine wilting disease by the insect and nematode and oak wilting by the insect and fungi
have been spreading mainly in western Japan for several decades, and now it has become so
serious problem in forestry. Pinus densiflora forest in low land mostly disappeared in the
southwest and reaches to northern most area of Honshu. Pinus thunbergii forest which had
been planted along the seacoast to prevent natural disasters was also declining. Therefore, the
practical methods of the rehabilitation and reforestation of pine forest have been expected
eagerly in rural areas.
Mycorrhiza formation is essential to Pinus species which generate the forests as a pioneer
plant at the dry site with infertile soil. These fungi also prefer to propagate in dry and infertile
soil condition. Therefore, it has been well known through the ecological study of pine forest (2)
that the man-made pine forest should be kept at the primary stage of plant succession by
cutting all of under shrubs and raking out the litter layer.
Ogawa M. proposed to rehabilitate and reforest the coastal pine forest using charcoal and
mycorrhizal fungi publishing a monograph (41). In the established forest, the same methods
described previously have been applied. Meanwhile, in the place from which all of pine tree
entirely destroyed, the under shrubs and top soil are completely removed before planting.
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Then pine seedlings with the inoculated mycorrhizal fungi, Rhizopogon, Pithoritus, Suillus
species, are planted together with the charcoal powder. The survival rates of these seedlings
were much higher than that without mycorrhiza and charcoal.
As such a trial, growing tree and burying charcoal, seems to be one of the practical methods
for carbon sequestration, Ogawa M. and his colleagues have promoted the movement to make
revive “White Sand and Green Pine” which is one of the symbolic scenery of Japan in order to
contribute the prevention of natural disasters and the countermeasure for global warming.
Ogawa M. who was working in the rehabilitation project of tropical rain forest in 1989 found
that a dominant species, Dipterocarpaceae, forms the ectomycorrhiza with several fungal
species among which Scleroderma columnare enhanced the seedling growth efficiently in
nursery. He tested the effect of charcoal powder on the growth of Shorea species and found
that the small amount of charcoal 2 % in volume was effective to stimulate the mycorrhizal
formation and the growth (42). Kikuti J. and M. Ogawa (43) devised the practical inoculation
method in which several saplings with the mycorrhiza were planted inside the nursery bed
and the pots were set under the canopy. By this method the mycelium of mycorrhizal fungi
penetrates through holes of the pot and naturally infected. Mori S. et al. (44) found the rice
husk charcoal is also effective and established the more convenient method. Rice husk
charcoal is not so harmful even if it was added too much.
The nursery technique to inoculate the mycorrhizal fungi with charcoal was also used in the
forestation project of pine in northern China and obtained the successful results (45). The
material such as charcoal which has higher water holding capacity is efficient to stimulate the
rooting and to supply water to the root through mycorrhiza even under severe dry condition. It
can be expected the charcoal will be used in dry land farming like date palm plantation and
the greening to stop the desertification (46).
Charcoal powder had been commonly used to cure the intestinal disorders of animals. In
1980s the utilization of charcoal and wood vinegar extended into the fields of animal
husbandry and the fish aquaculture. One of the wood vinegar makers invented in 1970s the
tablet of charcoal powder containing wood vinegar and sold as a medicine of live stocks being
formally recognized MAFF (33). When animals take the drug with the feed, it is said that the
quality of meat, fat and egg can be improved being affected with the high activity of intestinal
microorganisms (47). Recently the use for pig and poultry increased to avoid the antibiotics
and to prevent the epidemics.
In general, charcoal powder has the strong ability to absorb the smell of excretions and
liquid. Especially the charcoal carbonized under lower temperature than 300 degree Celsius
shows the strong adsorption of ammonium (48). The mixture of charcoal and wood vinegar has
been used in barn as the deodorant and absorbent of liquid. It seems that these effects result
from the complex reactions of charcoal and wood vinegar, but there is a few available scientific
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data (33).
The material containing wood vinegar also is used in the aquaculture of eel and fish to keep
water clean (33). Sometimes high quality charcoal which is carbonized under higher
temperature has been also used for water purification in the fish tank. From experiences it is
said that fish likes to spawn around the charcoal, probably because some algae propagate on
the wood charcoal and carbon fiber
In 2000, the fundamental law concerning to the establishment of recycling social system was
enacted in Japan, and it was acquired to reuse any wastes as much as possible. Particularly
the incineration of waste woods was prohibited in order to reduce the discharge of CO2 and
dioxin. The total amount of waste woods mainly from construction has reached to 4.6 million
ton per year, but the domestic use is only 60 % still now. Therefore, some construction
companies have switched from the incineration to the carbonization and intended to use the
charcoal not only in agriculture but also for the humidity control of house and building,
because it is necessary to reduce the high humidity of traditional wooden building in Japan.
The function of charcoal for humidity control was studied intensively for several decades ago
(49) (50). Recently the construction companies have begun to spread the charcoal bag not only
over the under floor but above the ceiling (51). Meanwhile it was also reported that the
treatment was efficient to reduce an asthma and atopic dermatitis by diminishing the
population of molds and tick (52) (53).
Recently the raw materials of charcoal are ranging from waste woods to some flammable
substances. Among them the carbonization of bamboo and its utilization has been widely
noticed as one of the dealing methods of bamboo forest which is recently occupying the wide
ranges in southwest Japan. Bamboo charcoal with somewhat different structure and functions
from wood charcoal has been used for the purification of water and air.
Up to several years ago, all of garbage from urban life had been burned in the incineration
plant, but now some cities began to carbonize the garbage and try its utilization. But there are
some problems to be solved, because the water content is usually so high that it consumes too
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much energy for desiccation, and some products are unsuitable for agricultural use because of
the high concentration of heavy metals and salt (54). Therefore, the thermal electric power
plants have tried to burn the garbage charcoal mixing with coal and oil (55). The wastes
disposed from food processing and live stock excretions have been also carbonized and used in
agriculture with compost (55).
On January 8 in 1991, Ogawa M. puts forward a new idea “The earth’s green saved with
charcoal” writing an article in Nihon Keizai Shinbun (Nikkei). He described in this paper the
outline of this concept; The carbon dioxide emitted into air can be fixed by photosynthesis into
the planted tree; If the waste wood will be carbonized and used in agriculture and other fields,
a vast amount of carbon will be stocked for long term in soil, and at the same time the
sustainable production of crops and trees will be realized.
In 1990s it has been recognized gradually in Japan that the carbonization are meaningful as a
counter measure against global warming through the production of renewable energy and the
uses for soil amendment in agriculture. However, the raw materials of carbonization in this
project must be restricted only the plant residues, because it induces large scale deforestation
as well as other biomass energy productions.
After COP3, Ogawa M. (56) (57) proposed the idea “Carbon Sequestration by Forestation
and Carbonization (CSFC Project)” in Japan and Asia. In Indonesia and Malaysia, the large
scale plantations of Acacia mangium for paper pulp and that of oil palm for biomass energy
are expanding after clear cutting of the natural forests. Fast growing species in monoculture
has been cut in rotation of every 8 to 10 years, and still now the slash burn fields are also
spreading in wide area. The sustainability of tree plantation and cropland in tropical region
has always become very serious problem. It needs to develop the more efficient techniques for
soil amendment to sustain the high productivity. It is certain that the charcoal use is one of
the most reliable and low-cost procedures being harmonized the nature. The same opinion was
proposed in the review written by Glaser B. et al. (58).
If charcoal is easily weathered in field, the idea may be meaningless. But it has been actually
exhibited that the charcoal has remained for one thousand years or more without weathering
at the ruin of ancient coin studio and in the old tombs in Japan and Korea.
After the observation of stability in sulfuric acid, sodium hydrate or under ultra violet light
for short term (personal communication), Kawamoto K. et al. (59) examined the durability of
wood charcoal against ozone and estimated the half-life of the charcoal in air. The weight of
saw dust charcoal carbonized at 400ºC was not affected with 8.5% ozone, while the one done at
1000ºC burned with 4.9% ozone. There were observed minute pores on the surface of charcoal
carbonized at 1000ºC. The half-life of charcoal which was carbonized at 1000ºC and treated by
ozone in air was about 50,000 years. From these results it is suggested that wood charcoal is
stable on a geological time scale.
On the other hand, Yamato M. et al. (60) reported the changes in soil chemical properties
and the crop yields when the bark charcoal of Acacia mangium, which was made of waste from
pulp industry, was applied as soil amendment for the cultivation of maize, cowpea and peanut
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in Sumatra, Indonesia. The yields of maize and peanut significantly increased after the
application of bark charcoal under the fertilized condition in an infertile soil. The amount of
root and the colonization rate of A mycorrhiza increased especially in maize. The application
of charcoal improved the soil chemical properties by neutralizing soil pH and increasing total
nitrogen, available phosphate contents, cation exchange capacity, amount of exchangeable
cations and base saturation. Moreover, it induced the decreasing of exchangeable Al ion which
seems to be harmful for the root growth. The effects of charcoal application appeared more
evidently in tropical region than those in Japan. Root nodule formations of leguminous plants
were also stimulated by charcoal.
Formerly it was reported that the population of free living nitrogen fixing bacteria
increased around the charcoal buried in tropical soil (28). Probably a small amount of nitrogen
seems to be accumulated into soil by charcoal application also in slash burn cultivation.
According to these results in Indonesia, the feasibility study of CSFC project was conducted
with the existing project of an industrial plantation and pulp production by Okimori Y. et al.
(61) in Indonesia Sumatra as an example of Clean Development Mechanism (CDM) project. It
was prospected that a total of 368,000 t / year of biomass residue and waste which were
disposed from plantation and pulp mill could be transformed into charcoal of 77,000 t / year, if
conventional charcoal producing methods are used. It was also expected that the carbon
emission reduction by the project reaches to 62,000 t-C / year (or 230,000 t-CO2). In addition,
this project can contribute to local economy providing the employment chance for 2,600
people, and will make realize the sustainable industrial plantation by soil amendment with
charcoal.
A similar trial was conducted also in Indonesian JICA project as a small scale example, and
the research result was reported by JICA (62). In this project it was confirmed that the
applications of charcoal were efficient both for the seedling growth of Acacia and the tree
growth in field.
In Western Australia, the multipurpose project of mallee eucalyptus plantation has been
carried out by Oil Mallee Company and Shea S. (63) in order to prevent the salinization of
arable soil. Another feasibility study of the project was conducted by Ogawa M. et al. (64) in
West Australia joining to the existing project. They proposed to carbonize wood waste and to
use the charcoal for soil amendment in wheat field. In this study, it was prospected that the
total carbon sink would reach 1,035,450 Mg-C with 14 % by aboveground biomass, 33.1 % by
belowground biomass and 52 % by charcoal in soil, if the plantation will be kept for 35 years.
Meanwhile, the effects of eucalyptus charcoal on the growth and yield of wheat were evidently
confirmed by Paul J. (in printing).
The feasibility study of carbon sequestration in which various kinds of waste wood out of
construction, saw mill, trimmed branch and others were recycled by carbonization was
conducted by RITE (Research Institute of Environment and Industry) as summarized in the
previous paper(64). It was focused on the effective use of surplus heat from a garbage
incinerator for carbonizing woody materials. It was prospected from the study that the waste
wood of 936.0 Mg-C / year would be converted into the net carbon sink of 298.5 Mg-C / year by
carbonization, with the fixed carbon recovery of the system being 31.9 %.
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The life cycle assessment has been conducted also in Japan on the case of carbonization of
waste wood and the use of charcoal for construction and greening. By this study it was
certified that the CSFC project is significant and useful for carbon sequestration also in
carbon and energy balance (unpublished).
From these research results, it is expected that CSFC project will be recognized as a
concrete, easy and low cost counter measure when the global warming will intensify more
seriously in the near future. Today the charcoal uses in various fields are extending through
the release of technical informations, and the charcoal production industry is growing as one
of environment businesses not only in Japan but also among Asian countries.
Literature cited
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2. Ogawa M. (1978) “ Biology of Matsutake ” pp.333 Tsukiji Shokan, Tokyo (in Japanese)
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Sougou Kagaku Shuppan Tokyo (in Japanese)
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polluted soils in a golf course using degrading bacteria –enriched charcoal. Proceedings
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(52) Morita H. (2005) The effect of humid controlling charcoal on the environmental
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Dermatoallergology: 115.
(53) Taketani T. (2006) Evaluation of the effect of humid controlling charcoal on the
infantile bronchial asthma. Allergy 55
55(3, 4): 467
(54) Abe I. et al. (2001) “ Carbonization of all wastes ,urban wastes, sewage, garbage and
waste woods, and their utilization” Proceedings of the symposium on the production of
charcoal and activated charcoal from wastes and their utilization. pp. 294, NIS Inc. (in
Japanese)
(56) Ogawa M. (1998) Greening with symbiotic microorganisms and charcoal in desert
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(58) Glaser B et al. Ameliorating physical and chemical properties of highly weathered
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(61) Okimori Y. et al. (2003) Potential of CO2 emission reduction by carbonizing biomass
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(62) JICA (2002) “ Demonstration studies on carbon fixing forest management project ”.
pp. 20 with appendices, JICA
(63) Shea S. (1999) Potential for carbon sequestration and product displacement with oil
mallees, In Proceedings: The Oil Mallee Profitable Landcare Seminar, Oil Mallee
Association, Perth, Australia
Page 15 of 15
J. Japan. Soc. Hort. Sci. 63(3) : 529-535. 1994.
Summary
Effects of several kinds of charcoal applied to soil on citrus growth and vesicular-
arbuscular mycorrhizal (VAM) development were investigated. Satsuma mandarin (Citrus
unshiu Marc.) trees on trifoliate orange (Poncirus trifoliata Raf.) rootstocks were trans-
planted to root boxes using the soil mixed with charcoal derived from rice husk, citrus
juice sediment or western spruce bark. The trees were inoculated with the spores of Glomus
fasciculatum (Thaxter) Gerdemann and Trappe emend. Walker and Koske. Elongation of the
roots in the charcoal treatments was more vigorous than that in the charcoal-free control.
The fresh weigths of the root, shoot and the whole tree increased in response to charcoal
application. The intensity of VAM infection in any charcoal treatment was higher than
that in the control. In particular, the percentage of the infection in the rice husk charcoal
plot was 41.5 and P concentration in the leaf exceeded that of the control.
In a Citrus iyo orchard, the percentage of VAM infection was 52% in the rice husk
charcoal plot, the highest among plots. The intensity in the Bahia grass (Paspalum
notatum Flugge.) plot was next, followed by the third highest rate found in the abandoned
plot which had not been cultivated in recent years. The lowest percentage of VAM infec-
tion was in a clean-culture plot. A microscopic observation also revealed that in a
charcoal-treated plot there were many sites where VAM fungi infected the root.
529
530 T. Ishii and K. Kadoya
ing in P-deficient soil surpassed those of non-VAM coal were mixed in a proportion of 50 to 1 by
trees stressed by high temperatures in August weight. The pH and electric conductivity (EC) of
(Shrestha et al., 1992). Interestingly, an inocula- the mixtures were measured with a pH meter and
satsuma mandarin trees. In particular, it enhanced Two months after planting, the roots were
the Hunter's a/b value of peel color and the sugar treated with 50 g fresh weight of soil inoculum con-
content in juice (Ishii et al., 1992b). In the citrus taining 300 ~ 340 spores of Glomus fasciculatum .
orchards where high quality fruit was produced, The inoculum was obtained from greenhouse pot
the percentage of VAM infection in the root was cultures of Bahia grass inoculated with Glomus
very high (Shrestha et al., 1993). fasciculatum originally isolated from citrus
On the other hand, phytotoxic substances exist orchards in Matsuyama city, Ehime prefecture,
in the bark and sawdust extracts from several Japan. In 1988, each tree was fertilized with 6.4 g
woody forest species, especially in the bark ex- of N, 3.2 g of P, and 3.8 g of K per annum from a
tracts of hinoki cypress (Chamaecyparis obtusa mixture of ammonium sulfate, calcium phosphate,
Sieb. et Zucc. ex Endl.) which are condensed tan- and potassium sulfate, respectively; the P and K
nins (Ishii and Kadoya, 1993). In soils to which contents in the charcoal were first deducted. The
unfermented organic matter were added, ethylene control trees were supplied with 5 g of calcium
enough to inhibit the growth of citrus trees (Ishii weight) to improve the soil pH. A Hoagland minor
and Kadoya, 1984). The problem of growth inhibi- element solution (1 liter/tree) was administered to
tion is solved, however, if the organic matter with each trees. In 1989, P was excluded.
phytotoxic substances is first transformed into Roots appearing on the glass plates of root boxes
charcoal and then used as a soil amendment. were traced onto transparent plastic sheets from
The purpose of this study is to investigate which the root lengths were measured, using a
effects of several kinds of charcoal applied to soil personal computer equipped with an image proc-
on citrus growth and VAM development. essor (NEC mediagraph MG -10 with a stylus pen,
In this experiment, we examined the effects of ashed at 550 •Ž overnight, and the residues were
charcoal application on the growth and VAM de- dissolved in 2.4 N HC]. The P content was meas-
velopment of 'Aoshima' satsuma mandarin trees on ured colorimetrically by the method of Deniges
trifoliate orange rootstocks for two years. In early (1920, 1921). Undamaged feeder rootlets were
April of 1988, three two-year-old satsuma man- sampled and rinsed with distilled water for a few
darin trees per plot were transplanted individually seconds. After the rootlets were cut into 2 - cm seg-
to root boxes (40 cm × 40 cm × 40 cm) containing ments behind the growing tip, the segments were
the mixtures of river sand and a specific charcoal. immediately fixed in FAA (formalin: acetic acid:
Before planting, the roots were carefully washed 50% ethanol, 13 : 5 : 200, v/v/v). Ten segments
to remove the soil which had nourished the trees. per treatment, stained by the technique of Phillips
The control soil lacked charcoal. The charcoal and Hayman (1970), were analyzed for the intensi-
used was made by using a chimney (15 cm in dia- ty of VAM infection by light microscopy. The per-
meter and 1.8 m in length) with some holes for centage of VAM infection was calculated with the
Experiment 1.
Table 2. Effect of charcoal application on the growth of satsuma mandarin trees (Experiment 1) .
quently observed on/in citrus roots sampled from Fig. 1. Photomicrograph of VAM fungal structures in
the charcoal-treated plots (Fig. 1). The SEM photo-
Citrus iyo roots stained with typan blue.
micrographs also indicated that in the charcoal- a : fungal hyphae ( × 100), b : vesicle ( × 150), c :
treated plot there were many sites where VAM arbuscle ( × 600).
fungi infected and penetrated into the root (Figs. 2
and 3).
ment in the root were stimulated by applying char-
Discussion
coal to soil. This stimulation of citrus growth by
In Japan, it has long been known that charcoal charcoal is attributed to an increase in the percen-
is a very effective soil conditioner which promotes tage of VAM infection in the roots. Ogawa (1987)
plant growth. Charcoal application may result in also reported that the enhanced colonization by
improving physical properties of soil, its fertility, symbiotic microorganisms, such as Rhizobium and
and biological conditions. The present experiment VAM fungi, by charcoal application, invigorated
indicated that citrus growth and VAM develop- soybean plants.
J. Japan. Soc. Hort. Sci. 63(3) : 529-535. 1994. 533
Soc. Hort. Sci. 62 (Suppl. 1): 26-27. (In Japanese). ral Culture Association, 1988. (In Japanese).
Ishii, T., J. Hamada, K. Ishizaki, Y. H. Shrestha and K. Nemec, S. 1979. Response of six citrus rootstocks to
Kadoya. 1993. Effect of sod culture system by three species of Glomus , a mycorrhizal fungus.
Bahia grass (Paspalum notatum Flugge.) on The citrus industry 5 : 5-14.
vesicular-arbuscular mycorrhizal development of Ogawa, M. 1987. Mutualistic microorganisms at the
satsuma mandarin trees. J. Jap. Soc. Hort. Sci. 62 plant-soil interface. Rural Culture Association. (In
(Suppl. 2): 98-99. (In Japanese). Japanese).
Ishii, T. and K. Kadoya. 1993. Phytotoxic constituents Phillips, J. M. and D. S. Hayman. 1970. Improved proc-
in the bark and sawdust extracts of Chamaecyparis edures for clearing roots and staining parasitic
obtusa and Cryptomeria japonica and their effects on and vesicular-arbuscular mycorrhizal fungi for
the growth of seedlings of trifoliate orange (Ponci- rapid assessment of infection. Trans. Br. Mycol.
rus trifoliate Ref.) and rice (Oryza sativa L.). J. Jap. Soc. 55 : 158-161.
Soc. Hort. Sci. 53 : 320-330. Shrestha, Y. H., T. Ishii and K. Kadoya. 1992. Effect of
Karnovsky, M. J. 1965. A formaldehyde-glutaralde- vesicular-arbuscular (VA) mycorrhizal fungi on
hyde fixative of high osmolality for use in electron photosynthesis and transpiration, and the dis-
microscopy. J. Cell Biol. 27 : 137A-138A. tribution of photosynthates of fruit-bearing satsu-
Kobayashi, N. 1988. Factors affecting the germination ma mandarin trees. J. Jap. Soc. Hort. Sci. 62
of spores of Gigaspara margarita . Microorganisms (Suppl. 1): 28-29. (In Japanese).
31 : 13-28. Shrestha, Y. H., T. Ishii and K. Kadoya. 1993. A rela-
Krikun, J. and Y. Levy. 1980. Effect of vesicular tion of vesicular-arbuscular mycorrhizal develop-
arbuscular mycorrhiza on citrus growth and ment and fruit quality of satsuma mandarin. J. Jap.
mineral composition. Phytoparasitica 8 : 195-200. Soc. Hort. Sci. 62 (Suppl. 2): 96-97. (In Japanese).
Menge, J. A., E. L. V. Johnson and R. G. Platt. 1978. Tang, Z., Q. Zhang and S. Hou. 1984. The effects of
Mycorrhizal dependency of several citrus culti- mycorrhizal fungus on phosphate uptake by citrus
vars under three nutrient regimes. New Phytol. 81 in.red earth. Acta Mycologia Sinica 3 : 170-177.
: 553-559. Timmer, L. W. and R. F. Leyden. 1980. The relation-
Miyazaki, S. 1697. Nougyou-Zensho. In : Yamada, T., J. ship of mycorrhizal infection to phosphorus-in-
Iinuma, M. Oka and S. Morita (eds.). The complete duced copper deficiency in sour orange seedlings.
works of ancient agricultural books in Japan. Ru- New Phytol. 85 : 15-23.
炭 施 用 が カ ンキ ツの樹 体 生 長 お よびVA菌 根 形 成 に及 ぼ す影 響
石 井 孝 昭1・ 門 屋 一 臣2
1愛 媛 大 学 教 育 学 部790愛 媛 県 松 山 市 文 京 町3
2愛 媛 大 学 農 学 部790愛 媛 県 松 山 市 樽 味3 -5-7
摘 要
あ る い は カ ンキ ツ ジ ュ ー ス か す か ら作 っ た 炭 で 処 理 し ま た 葉 内 の リ ン 含 量 も増 加 した.一 方,宮 内 イ ヨカ ン
地 下 部 重 お よ び新 梢 重 も炭 施 用 区 で 増 大 し た.VA菌 順 で あ っ た.
Microbial Fertilizers in Japan 6/25/09 7:07 AM
Abstract
Introduction
In 1961, Japan enacted the "Fundamental Law of Agriculture", which
encouraged farmers to selectively produce vegetables, fruits, forage crops
and livestock as well as rice, instead of staple foods such as wheat, barley
and corn. The aim of the law was to raise farmers' incomes in response to the
rapid growth of the Japanese economy. Consumption of vegetables, fruits,
milk, eggs and meats increased with economic growth. Farmers adopted the
strategy of increasing crop yields by applying large amounts of chemical
fertilizers and pesticides. During the 1960s and 1970s, the yield of many
crops per unit area increased dramatically as the result of intensive use of
chemical inputs and various soil amendments.
At present, however, the yield of many crops in Japan has reached a plateau.
Moreover, the negative effects of heavy applications of chemical inputs are
becoming apparent, in terms of both production and the environment,
especially in the case of vegetables. Physiological disturbance of plant
metabolism is common, due to the accumulation of excess plant nutrients in
the soil. The spread of soil-borne diseases is a threat to vegetable production,
especially where monoculture is prevailing. Pollution of underground and
surface water by nitrates is sometimes reported from vegetable producing
areas. Quality deterioration, in terms of a decrease in the content of vitamins
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
The main incentive for farmers to use microorganisms seems to be that they
hope to increase the yield or quality of their crops at a relatively low cost,
without a large investment of money and labor. Although many microbial
materials are sold commercially, most of them are not microbiologically
defined, i.e. the microorganisms contained in the products are not identified,
and the microbial composition is not fixed. Many of these commercial
products are advertised as if they could solve any problem a farmer is likely
to encounter. Because most extension advisors lack any knowledge of
microbial products, confusion and trouble frequently occur.
The idea that the application of charcoal stimulates indigenous AMF in soil
and thus promotes plant growth is relatively well-known in Japan, although
the actual application of charcoal is limited due to its high cost. The concept
originated in the work of M. Ogawa, a former soil microbiologist in the
Forestry and Forest Products Research Institute in Tsukuba. He and his
colleagues applied charcoal around the roots of pine trees growing by the
seashore, and found that Japanese truffles became plentiful. He also tested
http://www.agnet.org/library/eb/430/ Page 2 of 16
Microbial Fertilizers in Japan 6/25/09 7:07 AM
seashore, and found that Japanese truffles became plentiful. He also tested
the application of charcoal to soybean with a small quantity of applied
fertilizer, and demonstrated the stimulation of plant growth and nodule
formation (Ogawa 1983). His findings with regard to legumes were taken up
for further study by the National Grassland Research Institute (Nishio and
Okano 1991).
Stimulation of Alfalfa Growth by Charcoal Application
Table 1 shows the results obtained with alfalfa in pot experiments. The soil
used was a volcanic ash soil with very low phosphate availability. Although
alfalfa growth was very poor without applied fertilizer, it was improved by the
application of small amounts of fertilizer, and even more by the application of
charcoal with the fertilizer.
Four sets of pots were prepared. Each set received the same amount of
fertilizer (2 g N, 4.4 g P and 8.3 g K/m2). Set [F] received only fertilizer. The
others received fertilizer and also rhizobia [F+R], 1,000g/m of charcoal
[F+C], and rhizobia plus charcoal [F+R+C]. The charcoal used was a
commercial product made of bark from several kinds of deciduous broad-
leaved trees. Particle composition was >2mm, 24%; 1-2mm, 18%, and
<1mm; 58%.
Compared to the sets which received fertilizer alone, or fertilizer plus rhizobia,
the charcoal application stimulated plant growth by 1.7 - 1.8 times [F+C] and
1.4 - 1.8 times [F+R+C], measured at 38 days after sowing. At this stage the
stimulatory effect of rhizobia on plant growth was not marked, because the
plants had met most of their requirements by absorbing the applied nitrogen
fertilizer, and nodule development was still at an early stage. At 58 days,
when the nitrate added had been completely exhausted, plants not inoculated
with rhizobia ([F] and [F + C]) ceased to grow, and their leaves turned yellow
due to nitrogen deficiency. The soil used did not contain any indigenous
rhizobia effective on alfalfa, so that roots not inoculated with R. meliloti did
not show any acetylene reduction activity. At this stage, the stimulatory effect
of charcoal on growth was observed only in the plants inoculated with
rhizobia. The shoot weight of the [F + R + C] plants was 1.7 times greater
than that of the [F + R] plants.
Stimulation of Nutrient Uptake by Charcoal Application
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
The relative values of the shoot fresh weight and the degree of AMF infection
were determined on the basis of the values of [F+R]. A significant correlation
was observed between the shoot weight and AMF infection (Fig. 2).
When the soil was sterilized by chloropicrin, alfalfa growth was greatly
reduced, even with the application of the same amount of fertilizer shown in
Table 1. The stimulatory effect of charcoal on plant growth also diminished.
On the other hand, vigorous plant growth and the stimulatory effects of
charcoal addition were clearly observed when the sterilized soil was mixed
with a large amount of native soil (Fig. 3). This clearly indicates that the
stimulatory effect of added charcoal may appear only when a certain level of
indigenous AMF are present.
Mechanism Whereby Charcoal Stimulates the
Growth of Amf
Charcoal may stimulate the growth of AMF by the following mechanism.
Charcoal particles have a large number of continuous pores with a diameter
of more than 100!m. They do not contain any organic nutrients, because of
the carbonization process. The large pores in the charcoal may offer a new
microhabitat to the AMF, which can obtain organic nutrients through mycelia
extended from roots. This may enable the AMF to extend their mycelia far out
from the roots, thus collecting a larger amount of available phosphate.
Utilization of Amf for Establishment of Green
Cover on Barren Land
Barren land with poor vegetation cover, such as bare slopes beside roads and
on mountains, or large fresh deposits of volcanic debris, are subject to serious
soil erosion. The ordinary method of establishing plant cover on sloping
barren land is to seed grass or transplant tree seedlings, together with
fertilization of the soil. At the early stages of plant development, however,
when plant cover is not yet well established, heavy rainfall can cause soil
erosion and leach out fertilizers. This retards plant establishment. To
overcome the problem, a new technology is now being developed.
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
much on flowers or fruit trees, although they probably will be in future. They
will probably not be used on low-value crops such as cereals, soybean and
pasture, because of the cost-benefit relationship.
In most cases, nursery beds are inoculated with AMF products, and the
inoculated seedlings are planted out in the field. Usually nursery beds also
receive 150-205 kg/ha of P2O5 fertilizer. Although this amount of phosphate
seems to be excessive in terms of producing full AMF activity, the growth of
seedlings has been reported to be increased significantly, by 20% or more, by
AMF inoculation. Final yields of marketable produce were reported to be
increased by 20-50%.
While more than 70% of total phosphate is present in organic forms, such as
inositol phosphate in volcanic ash soils, there are very few indigenous
microorganisms with a strong ability to decompose inositol phosphate in the
soil. On the contrary, Japanese soils contain many indigenous heterotrophic
microorganisms which solubilize mineral bound phosphates by the excretion
of chelating organic acids. In grassland soils, phosphate solubilizing
microorganisms made up 1% of bacterial populations and 10% of fungal
populations (Nishio 1985). Tinker (1980) raised doubts on the utilization of
heterorophic phosphate solubilizing microorganisms, because they need a
large amount of organic matter before they can excrete organic acids. Even if
phosphate is solubilized, phosphate ions are incorporated into the microbial
biomass, so roots cannot absorb enough of them. Thus, we adopted the
following strategy: a) The addition of a large amount of organic matter makes
phosphate solubilizing (PS) microorganisms proliferate and these solubilize
bound phosphate. b) Solubilized phosphates are incorporated into the
microbial biomass during other microbial multiplication, using organic matter.
c) Once the organic matter becomes exhausted, the microbial biomass
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
Each step described above has been experimentally confirmed (Kimura and
Nishio 1989). Fig. 4 shows the difference in biomass P (P retained in biomass)
between the soils with and without compound phosphate. When the soil was
incubated for 7 days by adding sucrose and ammonium sulfate, the biomass P
significantly increased, utilizing Ca-, Al-, and Fe-phosphates and low-quality
rock phosphate. However, no significant increase was observed with varicite
(crystallized aluminum phosphate) over this short period. This indicates that
insoluble phosphates which are not crystallized can be solubilized by
indigenous microorganisms when abundant carbon sources are supplied.
The rate of increase in soil biomass P fell, and available phosphate increased,
after the depletion of carbon sources, or after soil treatments such as
chloropicrin fumigation, air-drying or grinding (Fig. 5). This indicates that
after the exhaustion of organic matter, microbial biomass falls, releasing
phosphate into the soil, and that the release of available phosphate can be
accelerated by soil treatments.
In terms of the plant nutrient supply, there are two types of organic farming.
One provides plant nutrients from local resources, and the other uses
commercial organic fertilizers. Most organic farmers in Japan use the latter
type, i.e. commercial organic fertilizers, made from rape seed meal or
soybean meal (both residues of oil extraction), meat and fish meal, bone
meal etc. These supply sufficient plant nutrients to give relatively high yields.
Local resources include green manures, composted livestock manure etc.
Utilization of Microbial Materials to Make
&Quot;Bokashi&Quot;
Since the original ingredients are dried materials, there are not enough
microorganisms present to begin immediate decomposition of the organic
matter. To avoid anaerobic fermentation, with its unpleasant odor, the
compost is inoculated with aerobic microorganisms which multiply rapidly.
Because these microorganisms need oxygen and have no heat-tolerance, the
pile is mixed and spread every one or two days. During the process of
composting, easily decomposable organic matter is decomposed through the
production of microbial biomass, liberating ammonium ions. The ammonium is
retained on soil particles. The microbial biomass contributes to the slower
release of nutrients with the residual ingredients. Overall, the aim of the
process seems to be, firstly, to decompose substances which attract pests,
and secondly, to create a slower-acting organic fertilizer.
Although many microbial products are sold in Japan, except in a few special
cases, they are not microbiologically defined, i.e. the microorganisms they
contain are not identified, and merely described in terms of their hoped-for
results. Products which not only identify the microorganisms, but quantify
them, are very rare. Fortunately, the microorganisms effective in bokashi
production are not restricted to a special group, but are very common species
which can multiply rapidly in ordinary composting materials. No serious
problems have occurred in bokashi production, with one interesting exception.
Is &Quot;Em&Quot; Really an Effective Microorganism?
What is "EM"?
Apart from compost made from household wastes, farmers are also making
bokashi, using EM products under anaerobic conditions, from other ordinary
organic materials. Higa claims in his book that a revolution in agriculture is
possible, since the use of EM products increases greatly the yield of crops. For
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
possible, since the use of EM products increases greatly the yield of crops. For
example, rice fertilized with EM bokashi produced brown rice yields of more
than 12 mt/ha.
I. Goto and a colleague of Tokyo Agricultural University carried out some field
experiments in cooperation with the EM company. They analyzed EM bokashi
supplied by the company and also bokashi supplied by farmers, and showed
that the samples contained on average 40 kg N, 30 Kg P2O5 and 13 kg K2O
per 1000 kg, much the same as ordinary bokashi (Goto and Muramoto 1995).
EM recommends the application of 1000 kg/ha of EM bokashi, but the input of
40 kg of nitrogen contained in this amount is not sufficient for the full growth
of vegetables. Goto examined the crops of farmers who use EM bokashi, and
found that the yield of lettuce from 1000 kg of EM bokashi was much the
same as that from ordinary commercial organic fertilizer, when the nitrogen
levels were adjusted. He also found that farmers generally applied 30 mt/ha
of cattle manure in addition to the EM bokashi, and pointed out that the yields
obtained by the farmers may have been greatly supported by the manure.
When in fact vegetables were cultivated with only 1000 kg/ha EM bokashi
alone in the fields of the University, he found that the yields of many
vegetables were only half those obtained by ordinary practices (Muramoto
and Goto 1995). Later, researchers of EM reported that when the nitrogen
level was adjusted to 100 kg/ha, EM bokashi (2500 kg/ha) yielded the same
quantity of lettuce as chemical fertilizer (Iwahori et al. 1996). Therefore, they
insisted that the standard amount of EM bokashi which should be applied was
2500 kg/ha for lettuce, and criticized Goto for using an insufficient amount.
These experiments seem to show that EM bokashi is no revolutionary step
forward, because when it is used, vegetables need the same level of nitrogen
as when they are given chemical fertilizers. Goto claims that EM bokashi is
nothing but ordinary bokashi, and has no special qualities (Goto et al. 1996).
Utilization of Azolla in Organic Paddy Fields
Although Azolla has seldom been utilized by Japanese farmers, regardless of
experimental results in research institutes, the recent trend towards organic
farming shows signs of changing the situation. A common practice in organic
rice production is to release ducklings, usually hybrids of domestic ducks and
wild ones, into paddy fields. The webs of their feet disturb the soil surface in
the shallow water, and remove the young seedlings of weeds, thus controlling
weeds without herbicides. I. Watanabe, who studied Azolla at the
International Rice Research Institute, speculated that this soil disturbance
would suspend soil particles in the water, thus increasing the availability of
phosphate adsorbed on soil particles to Azolla floating on the water surface.
He made contact with a farmer and proposed his idea. They carried out
experiments in 1995 in the farmer's paddy field, inoculating Azolla in early
May without fertilizer. The Azolla increased very rapidly, and covered the
whole field just like a carpet. The Azolla biomass was estimated to be 28
mt/ha on June 25. Subsequently, some of the Azolla was eaten by birds, and
was reduced by about 30% by July 14. Since the Azolla supplied too much
nitrogen to the rice, some of the plants collapsed, and the yield of brown rice
was only 4.36-4.5 mt/ha (Huruno 1995). This experiment is likely to trigger
off widespread utilization of Azolla in Japan.
http://www.agnet.org/library/eb/430/ Page 10 of 16
Microbial Fertilizers in Japan 6/25/09 7:07 AM
Abstract
Introduction
In 1961, Japan enacted the "Fundamental Law of Agriculture", which
encouraged farmers to selectively produce vegetables, fruits, forage crops
and livestock as well as rice, instead of staple foods such as wheat, barley
and corn. The aim of the law was to raise farmers' incomes in response to the
rapid growth of the Japanese economy. Consumption of vegetables, fruits,
milk, eggs and meats increased with economic growth. Farmers adopted the
strategy of increasing crop yields by applying large amounts of chemical
fertilizers and pesticides. During the 1960s and 1970s, the yield of many
crops per unit area increased dramatically as the result of intensive use of
chemical inputs and various soil amendments.
At present, however, the yield of many crops in Japan has reached a plateau.
Moreover, the negative effects of heavy applications of chemical inputs are
becoming apparent, in terms of both production and the environment,
especially in the case of vegetables. Physiological disturbance of plant
metabolism is common, due to the accumulation of excess plant nutrients in
the soil. The spread of soil-borne diseases is a threat to vegetable production,
especially where monoculture is prevailing. Pollution of underground and
surface water by nitrates is sometimes reported from vegetable producing
areas. Quality deterioration, in terms of a decrease in the content of vitamins
http://www.agnet.org/library/eb/430/ Page 1 of 16
Microbial Fertilizers in Japan 6/25/09 7:07 AM
The main incentive for farmers to use microorganisms seems to be that they
hope to increase the yield or quality of their crops at a relatively low cost,
without a large investment of money and labor. Although many microbial
materials are sold commercially, most of them are not microbiologically
defined, i.e. the microorganisms contained in the products are not identified,
and the microbial composition is not fixed. Many of these commercial
products are advertised as if they could solve any problem a farmer is likely
to encounter. Because most extension advisors lack any knowledge of
microbial products, confusion and trouble frequently occur.
The idea that the application of charcoal stimulates indigenous AMF in soil
and thus promotes plant growth is relatively well-known in Japan, although
the actual application of charcoal is limited due to its high cost. The concept
originated in the work of M. Ogawa, a former soil microbiologist in the
Forestry and Forest Products Research Institute in Tsukuba. He and his
colleagues applied charcoal around the roots of pine trees growing by the
seashore, and found that Japanese truffles became plentiful. He also tested
http://www.agnet.org/library/eb/430/ Page 2 of 16
Microbial Fertilizers in Japan 6/25/09 7:07 AM
seashore, and found that Japanese truffles became plentiful. He also tested
the application of charcoal to soybean with a small quantity of applied
fertilizer, and demonstrated the stimulation of plant growth and nodule
formation (Ogawa 1983). His findings with regard to legumes were taken up
for further study by the National Grassland Research Institute (Nishio and
Okano 1991).
Stimulation of Alfalfa Growth by Charcoal Application
Table 1 shows the results obtained with alfalfa in pot experiments. The soil
used was a volcanic ash soil with very low phosphate availability. Although
alfalfa growth was very poor without applied fertilizer, it was improved by the
application of small amounts of fertilizer, and even more by the application of
charcoal with the fertilizer.
Four sets of pots were prepared. Each set received the same amount of
fertilizer (2 g N, 4.4 g P and 8.3 g K/m2). Set [F] received only fertilizer. The
others received fertilizer and also rhizobia [F+R], 1,000g/m of charcoal
[F+C], and rhizobia plus charcoal [F+R+C]. The charcoal used was a
commercial product made of bark from several kinds of deciduous broad-
leaved trees. Particle composition was >2mm, 24%; 1-2mm, 18%, and
<1mm; 58%.
Compared to the sets which received fertilizer alone, or fertilizer plus rhizobia,
the charcoal application stimulated plant growth by 1.7 - 1.8 times [F+C] and
1.4 - 1.8 times [F+R+C], measured at 38 days after sowing. At this stage the
stimulatory effect of rhizobia on plant growth was not marked, because the
plants had met most of their requirements by absorbing the applied nitrogen
fertilizer, and nodule development was still at an early stage. At 58 days,
when the nitrate added had been completely exhausted, plants not inoculated
with rhizobia ([F] and [F + C]) ceased to grow, and their leaves turned yellow
due to nitrogen deficiency. The soil used did not contain any indigenous
rhizobia effective on alfalfa, so that roots not inoculated with R. meliloti did
not show any acetylene reduction activity. At this stage, the stimulatory effect
of charcoal on growth was observed only in the plants inoculated with
rhizobia. The shoot weight of the [F + R + C] plants was 1.7 times greater
than that of the [F + R] plants.
Stimulation of Nutrient Uptake by Charcoal Application
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The relative values of the shoot fresh weight and the degree of AMF infection
were determined on the basis of the values of [F+R]. A significant correlation
was observed between the shoot weight and AMF infection (Fig. 2).
When the soil was sterilized by chloropicrin, alfalfa growth was greatly
reduced, even with the application of the same amount of fertilizer shown in
Table 1. The stimulatory effect of charcoal on plant growth also diminished.
On the other hand, vigorous plant growth and the stimulatory effects of
charcoal addition were clearly observed when the sterilized soil was mixed
with a large amount of native soil (Fig. 3). This clearly indicates that the
stimulatory effect of added charcoal may appear only when a certain level of
indigenous AMF are present.
Mechanism Whereby Charcoal Stimulates the
Growth of Amf
Charcoal may stimulate the growth of AMF by the following mechanism.
Charcoal particles have a large number of continuous pores with a diameter
of more than 100!m. They do not contain any organic nutrients, because of
the carbonization process. The large pores in the charcoal may offer a new
microhabitat to the AMF, which can obtain organic nutrients through mycelia
extended from roots. This may enable the AMF to extend their mycelia far out
from the roots, thus collecting a larger amount of available phosphate.
Utilization of Amf for Establishment of Green
Cover on Barren Land
Barren land with poor vegetation cover, such as bare slopes beside roads and
on mountains, or large fresh deposits of volcanic debris, are subject to serious
soil erosion. The ordinary method of establishing plant cover on sloping
barren land is to seed grass or transplant tree seedlings, together with
fertilization of the soil. At the early stages of plant development, however,
when plant cover is not yet well established, heavy rainfall can cause soil
erosion and leach out fertilizers. This retards plant establishment. To
overcome the problem, a new technology is now being developed.
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
much on flowers or fruit trees, although they probably will be in future. They
will probably not be used on low-value crops such as cereals, soybean and
pasture, because of the cost-benefit relationship.
In most cases, nursery beds are inoculated with AMF products, and the
inoculated seedlings are planted out in the field. Usually nursery beds also
receive 150-205 kg/ha of P2O5 fertilizer. Although this amount of phosphate
seems to be excessive in terms of producing full AMF activity, the growth of
seedlings has been reported to be increased significantly, by 20% or more, by
AMF inoculation. Final yields of marketable produce were reported to be
increased by 20-50%.
While more than 70% of total phosphate is present in organic forms, such as
inositol phosphate in volcanic ash soils, there are very few indigenous
microorganisms with a strong ability to decompose inositol phosphate in the
soil. On the contrary, Japanese soils contain many indigenous heterotrophic
microorganisms which solubilize mineral bound phosphates by the excretion
of chelating organic acids. In grassland soils, phosphate solubilizing
microorganisms made up 1% of bacterial populations and 10% of fungal
populations (Nishio 1985). Tinker (1980) raised doubts on the utilization of
heterorophic phosphate solubilizing microorganisms, because they need a
large amount of organic matter before they can excrete organic acids. Even if
phosphate is solubilized, phosphate ions are incorporated into the microbial
biomass, so roots cannot absorb enough of them. Thus, we adopted the
following strategy: a) The addition of a large amount of organic matter makes
phosphate solubilizing (PS) microorganisms proliferate and these solubilize
bound phosphate. b) Solubilized phosphates are incorporated into the
microbial biomass during other microbial multiplication, using organic matter.
c) Once the organic matter becomes exhausted, the microbial biomass
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
Each step described above has been experimentally confirmed (Kimura and
Nishio 1989). Fig. 4 shows the difference in biomass P (P retained in biomass)
between the soils with and without compound phosphate. When the soil was
incubated for 7 days by adding sucrose and ammonium sulfate, the biomass P
significantly increased, utilizing Ca-, Al-, and Fe-phosphates and low-quality
rock phosphate. However, no significant increase was observed with varicite
(crystallized aluminum phosphate) over this short period. This indicates that
insoluble phosphates which are not crystallized can be solubilized by
indigenous microorganisms when abundant carbon sources are supplied.
The rate of increase in soil biomass P fell, and available phosphate increased,
after the depletion of carbon sources, or after soil treatments such as
chloropicrin fumigation, air-drying or grinding (Fig. 5). This indicates that
after the exhaustion of organic matter, microbial biomass falls, releasing
phosphate into the soil, and that the release of available phosphate can be
accelerated by soil treatments.
In terms of the plant nutrient supply, there are two types of organic farming.
One provides plant nutrients from local resources, and the other uses
commercial organic fertilizers. Most organic farmers in Japan use the latter
type, i.e. commercial organic fertilizers, made from rape seed meal or
soybean meal (both residues of oil extraction), meat and fish meal, bone
meal etc. These supply sufficient plant nutrients to give relatively high yields.
Local resources include green manures, composted livestock manure etc.
Utilization of Microbial Materials to Make
&Quot;Bokashi&Quot;
Since the original ingredients are dried materials, there are not enough
microorganisms present to begin immediate decomposition of the organic
matter. To avoid anaerobic fermentation, with its unpleasant odor, the
compost is inoculated with aerobic microorganisms which multiply rapidly.
Because these microorganisms need oxygen and have no heat-tolerance, the
pile is mixed and spread every one or two days. During the process of
composting, easily decomposable organic matter is decomposed through the
production of microbial biomass, liberating ammonium ions. The ammonium is
retained on soil particles. The microbial biomass contributes to the slower
release of nutrients with the residual ingredients. Overall, the aim of the
process seems to be, firstly, to decompose substances which attract pests,
and secondly, to create a slower-acting organic fertilizer.
Although many microbial products are sold in Japan, except in a few special
cases, they are not microbiologically defined, i.e. the microorganisms they
contain are not identified, and merely described in terms of their hoped-for
results. Products which not only identify the microorganisms, but quantify
them, are very rare. Fortunately, the microorganisms effective in bokashi
production are not restricted to a special group, but are very common species
which can multiply rapidly in ordinary composting materials. No serious
problems have occurred in bokashi production, with one interesting exception.
Is &Quot;Em&Quot; Really an Effective Microorganism?
What is "EM"?
Apart from compost made from household wastes, farmers are also making
bokashi, using EM products under anaerobic conditions, from other ordinary
organic materials. Higa claims in his book that a revolution in agriculture is
possible, since the use of EM products increases greatly the yield of crops. For
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Microbial Fertilizers in Japan 6/25/09 7:07 AM
possible, since the use of EM products increases greatly the yield of crops. For
example, rice fertilized with EM bokashi produced brown rice yields of more
than 12 mt/ha.
I. Goto and a colleague of Tokyo Agricultural University carried out some field
experiments in cooperation with the EM company. They analyzed EM bokashi
supplied by the company and also bokashi supplied by farmers, and showed
that the samples contained on average 40 kg N, 30 Kg P2O5 and 13 kg K2O
per 1000 kg, much the same as ordinary bokashi (Goto and Muramoto 1995).
EM recommends the application of 1000 kg/ha of EM bokashi, but the input of
40 kg of nitrogen contained in this amount is not sufficient for the full growth
of vegetables. Goto examined the crops of farmers who use EM bokashi, and
found that the yield of lettuce from 1000 kg of EM bokashi was much the
same as that from ordinary commercial organic fertilizer, when the nitrogen
levels were adjusted. He also found that farmers generally applied 30 mt/ha
of cattle manure in addition to the EM bokashi, and pointed out that the yields
obtained by the farmers may have been greatly supported by the manure.
When in fact vegetables were cultivated with only 1000 kg/ha EM bokashi
alone in the fields of the University, he found that the yields of many
vegetables were only half those obtained by ordinary practices (Muramoto
and Goto 1995). Later, researchers of EM reported that when the nitrogen
level was adjusted to 100 kg/ha, EM bokashi (2500 kg/ha) yielded the same
quantity of lettuce as chemical fertilizer (Iwahori et al. 1996). Therefore, they
insisted that the standard amount of EM bokashi which should be applied was
2500 kg/ha for lettuce, and criticized Goto for using an insufficient amount.
These experiments seem to show that EM bokashi is no revolutionary step
forward, because when it is used, vegetables need the same level of nitrogen
as when they are given chemical fertilizers. Goto claims that EM bokashi is
nothing but ordinary bokashi, and has no special qualities (Goto et al. 1996).
Utilization of Azolla in Organic Paddy Fields
Although Azolla has seldom been utilized by Japanese farmers, regardless of
experimental results in research institutes, the recent trend towards organic
farming shows signs of changing the situation. A common practice in organic
rice production is to release ducklings, usually hybrids of domestic ducks and
wild ones, into paddy fields. The webs of their feet disturb the soil surface in
the shallow water, and remove the young seedlings of weeds, thus controlling
weeds without herbicides. I. Watanabe, who studied Azolla at the
International Rice Research Institute, speculated that this soil disturbance
would suspend soil particles in the water, thus increasing the availability of
phosphate adsorbed on soil particles to Azolla floating on the water surface.
He made contact with a farmer and proposed his idea. They carried out
experiments in 1995 in the farmer's paddy field, inoculating Azolla in early
May without fertilizer. The Azolla increased very rapidly, and covered the
whole field just like a carpet. The Azolla biomass was estimated to be 28
mt/ha on June 25. Subsequently, some of the Azolla was eaten by birds, and
was reduced by about 30% by July 14. Since the Azolla supplied too much
nitrogen to the rice, some of the plants collapsed, and the yield of brown rice
was only 4.36-4.5 mt/ha (Huruno 1995). This experiment is likely to trigger
off widespread utilization of Azolla in Japan.
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Plant and Soil 244: 273–279, 2002.
© 2002 Kluwer Academic Publishers. Printed in the Netherlands.
273
Abstract
Inoculation of arbuscular mycorrhizal (AM) fungi has potential benefits in not only sustainable crop production
but also environmental conservation. However, the difficulty of inoculum production due to the obligate biotrophic
nature of AM fungi has been the biggest obstacle to putting inoculation into practice. Nevertheless, several compan-
ies have sought to produce inoculum of AM fungi. Firstly in this review, the present status of inoculum production
and its use in Japan is described. Secondly, although the effectiveness of inoculation is primarily limited by environ-
mental and biological factors, some possible ways to improve inoculation performance are discussed. Approaches
include use of chemicals to increase spore germination and colonization and soil application of charcoal to provide
a microhabitat for AM fungi to colonize and survive.
The Ministry of Agriculture, Forestry and Fisher- AM fungal species, and the handling of inoculum into
ies (MAFF) of the Japanese Government has promoted horticultural practices.
the introduction of various technologies to reduce The cost of inoculum production is a serious prob-
agrochemical inputs to arable lands for sustainable lem because the inocula are not competitive in price
agriculture. MAFF recognized that AM inocula are with phosphorus fertilizer. Even if farmers understand
useful to reduce phosphate fertilizer application, and the significance of sustainable agricultural systems,
in 1996 approved AM inocula as soil amendments the reduction of phosphorus inputs by using AM
by an ordinance of the Soil Productivity Improve- fungal inocula alone cannot justify the use of the
ment Law. The ordinance regulates the quality of 12 inocula except in the case of high value crops. An-
types of amendments such as zeolite, peat, and other other serious problem is control of phytopathogenic
organic/inorganic materials that are effective for the micro-organisms. At present, the inoculum produced
improvement of soil productivity. The ordinance spe- is not completely free from pathogens, even though the
cifies that a quality guarantee be labeled on the outside producers attempt to control pathogens with various
of the product container. In the case of AM fungi, the agrochemicals. Farmers are very aware of the risk of
following items are required; (i) name and address of pathogens, so they do not accept inoculum containing
producer, (ii) raw materials, (iii) symbiotic efficiency, host root residues. Although pieces of root colonized
(iv) efficacy, (v) recommended application rate, (vi) with AM fungi, especially Glomus intraradices and
storage conditions, (vii) expiration date. In item (ii), related species, function well as propagules, the com-
carrier material, such as peat or zeolite, is indicated. panies remove such residue of host roots from their
In item (iii), the symbiotic efficiency is expressed as products.
percentage of colonization by the inoculum of a spe-
cific test plant such as Welsh onion under standard
conditions. In item (iv), the producer should note that Rehabilitation of a volcanic deposit-affected area
the inoculum is not effective for some crops species
belonging to the Brassicaceae and Chenopodiaceae, Inocula of AM fungi are expected to be substantially
and that the inoculum may not be effective in soils beneficial in the establishment of vegetation in de-
rich in available phosphate. This quality guarantee is graded or bare landscapes (Miller and Jastrow, 1992;
important to expel poor quality microbial inocula from Pfleger et al., 1994; Requena et al., 2001). Currently
the market place. in Japan, AM fungal inocula has been applied most
At present, three companies, Central Glass Co., successfully in revegetation of land by devastated by
Idemitsu Kosan Co., and Osaka Gas Co., produce volcanic activities (Marumoto et al., 1996, 1999).
AM inoculum. The MAFF statistics indicate that 28 In the Japanese islands, active volcanos sometimes
– 83 tons of the inocula were supplied per year from seriously damage large areas and destroy human activ-
1997 to 1999. Much of inoculum was supplied for ities. Newly deposited volcanic materials are very low
non-agricultural applications such as rehabilitation of in nutrients available for plants and very susceptible to
degraded or devegetated landscapes. Because enduse erosion. The revegetation process is therefore slow, so
of the inocula is not within the framework of the or- the acceleration of revegetation is required not only for
dinance, the above statistics do not include the supply environmental conservation but also for the prevention
for such non-agricultural objectives. of erosion. In 1990, Mt. Fugendake (32◦ 45 N, 130◦
Although the detailed procedure for inoculum pro- 19 E) began volcanic activities after 200 years of in-
duction is proprietary, these inocula are produced un- activity. During 1991 – 1994, several large pyroclastic
der glasshouse conditions based upon the pot culture flows completely destroyed the previous vegetation on
technique (Jarstfer and Sylvia, 1993). One company the mountain slope. More than 1000 ha of the moun-
uses expanded clay as a potting medium (Dehne and tain slope and the base of the mountain were covered
Backhaus, 1986). Others extract and concentrate the with a thick pyroclastic deposit.
propagules of AM fungi from potting media, and car- Immediately after volcanic activities ceased in
riers such as peat are mixed with the propagules. The 1995, a revegetation project was started. Because the
inocula are mainly sold to horticulture farmers. Some area to be revegetated was on a steep slope of the vol-
formulations are specific for each crop species by tak- cano and was still a hazard, the workers were not able
ing into account factors such as host plant species, to access the revegetation project site during the first
a few years. Therefore, revegetation materials were
275
Figure 1. Revegetation in a volcano-devastated area of Mt. Fugendake, Japan. (A) Application of bags containing AM fungal inoculum on
the pyroclastic flow. (B) Germination of plants from seeds contained in the bag. (C) A landscape of the pyroclastic flow 3 weeks after the
application. (D) A landscape in the same site as (C) 3 years after the application.
Spore germination
Growth of extraradical hyphae and sporulation spores for research purposes (Glomales in vitro col-
lection; http://www.mbla.ucl.ac.be/ginco-bel/anglais
Nutrient absorption of mycorrhizal plants from soil /cadre.htm) but is unsuitable for commercial inoculum
depends upon the function of extraradical hyphae. Soil production. Even if mass production system of the
management that assures the extraradical hyphae to dual culture of lower production cost was developed
be fully functioning may enable improvement of in- (Jolicoeur et al., 1999), it is uncertain whether the use
oculation performance. Application of charcoal to soil of spores produced from roots transformed by a patho-
stimulated the colonization of crops by indigenous genic bacterium, Agrobacterium rhizogenes, would be
AM fungi (Nishio and Okano, 1991; Ogawa et al., allowed for inoculation in field.
1983; Saito, 1990) (Figure 4). The effect of char- In the field application of any microbial inoculum,
coal was ascribed to its physioco-chemical properties. it is essential to verify that the inoculated micro-
Charcoal is porous, weakly alkaline, and does not organisms caused the plant response in field. Various
serve as a substrate for saprophytes. AM fungi sensit- molecular techniques have been developed to dis-
ive to competition from saprophytes can easily extend tinguish the inoculated strain from other indigenous
their extraradical hyphae into charcoal buried in soil strains. However, these techniques to identify AM
and sporulate in the particles (Ogawa, 1987). Charcoal fungi are still not routinely used because of genetic
particles act as a micro-habitat for AM fungi to survive heterogeneity in AM fungi. Although ITS (internal
and later grow into the soil, which makes charcoal transcribed spacer) sequence of rDNA is widely used
suitable as a carrier of AM fungal inoculum (Ogawa, for discrimination among strains in other fungal taxa,
1989). Charcoal can be applied in a large scale in in- application of the ITS sequence for identification of
fertile soils rich in indigenous AM fungi, but its cost AM fungi is complicated. For example, ITS sequences
is not competitive with inorganic fertilizers at least in of 3 isolates of G. margarita including BEG34 and
Japan. two Japanese isolates showed that the sequences were
Although many inoculation studies have been con- too diverse to discriminate the isolates; the accession
ducted, there is still little known about how AM fungi number of the sequence data used were AJ006838–50
proliferate and survive in soil and how they affect for isolates BEG34, AB048619–29 for MAFF520052,
the following crop. In arable lands, various crops are and AB048607–18 for MAFF520054, respectively
cultivated in sequence. Absence of a host plant, cul- (Saito, 2000). Single stranded conformation poly-
tivation of non-host crops, or long fallow negatively morphism (SSCP) of the large ribosomal subunit gene
affect the population of AM fungi in soil (Kurle and may be promising to discriminate isolates of several
Pfleger, 1994; Safir, 1994; Thompson, 1987). On Glomus spp. (Kjøller and Rosendahl, 2000), while
the other hand, some mycotrophic crops increase the the sequence diversity in this region is very high
growth of the succeeding mycotrophic crop (Arihara (Clapp et al., 2001). We need more reliable molecu-
and Karasawa, 2000; Karasawa et al., 2001). Irrespect- lar techniques to trace the inoculated fungi. Therefore,
ive of inoculation, therefore, crop sequence should be from the standpoint of not only basic biological in-
taken into account when predicting the responses of terest but also application, molecular genetics of these
AM fungi in a sustainable agricultural system. multinucleate fungi is of high research priority.
It is now well recognized that inoculation of AM
fungi has a potential significance in not only sustain-
Future prospects able crop production, but also environmental conser-
vation. However, the status quo of inoculation is far
Commercial inoculum production of AM fungi has from practical technology that can be widely used in
been increasing during the past decade, although the field. Together, a basic understanding of the bio-
the future prospect of the business is still uncer- logy of AM fungi and an improvement in inoculum
tain. The obligate biotrophic nature of AM fungi production and inoculation technology are required to
inevitably raises the cost for inoculum produc- advance management of these fungi.
tion. Soilless culture systems seem to be prom-
ising, because this enables the production of clean
spores (Jarstfer and Sylvia, 1999). A dual culture Acknowledgements
of transformed carrot hairy root with AM fungi
is an excellent system for providing the sterile The preparation of this paper was supported in part by
278
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Biosciences (PROBRAIN), Bio-oriented Technology Bioengineer. 63, 224–232.
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Research Advancement Institution, Japan. The authors growth and arbuscular mycorrhizal colonization of maize plants
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Co. Ltd., and Osaka Gas Co. Ltd. for valuable inform- 286–293.
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Soil Biology & Biochemistry 41 (2009) 1301–1310
Effect of biochar amendment on soil carbon balance and soil microbial activity
S. Steinbeiss a, *, G. Gleixner a, M. Antonietti b
a
Max Planck Institute for Biogeochemistry, Hans-Knoell-Str. 10, 07745 Jena, Germany
b
Max Planck Institute of Colloids and Interfaces, Am Muehlenberg 1, 14476 Potsdam-Golm, Germany
a r t i c l e i n f o a b s t r a c t
Article history: We investigated the behavior of biochars in arable and forest soil in a greenhouse experiment in order
Received 28 July 2008 to prove that these amendments can increase carbon storage in soils. Two qualities of biochar were
Received in revised form produced by hydrothermal pyrolysis from 13C labeled glucose (0% N) and yeast (5% N), respectively. We
16 March 2009
quantified respiratory losses of soil and biochar carbon and calculated mean residence times of the
Accepted 21 March 2009
Available online 17 April 2009
biochars using the isotopic label. Extraction of phospholipid fatty acids from soil at the beginning and
after 4 months of incubation was used to quantify changes in microbial biomass and to identify
microbial groups utilizing the biochars. Mean residence times varied between 4 and 29 years,
Keywords:
Biochar depending on soil type and quality of biochar. Yeast-derived biochar promoted fungi in the soil, while
13
C labeling glucose-derived biochar was utilized by Gram-negative bacteria. Our results suggest that residence
PLFA times of biochar in soils can be manipulated with the aim to ‘‘design’’ the best possible biochar for
Residence times a given soil type.
Greenhouse experiment Ó 2009 Elsevier Ltd. All rights reserved.
0038-0717/$ – see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.soilbio.2009.03.016
1302 S. Steinbeiss et al. / Soil Biology & Biochemistry 41 (2009) 1301–1310
combining fertilizer and carbon storage function in soils would 2.2. Biochar production and characterization
activate the microbial community leading to nutrient release and
fertilization and would add to the decadal soil carbon pool. The Stable carbon isotopes have proven to reliably trace the flow of
structural and chemical properties of biochars that are driving carbon in various soil organic matter pools (Gleixner et al., 2001)
their decomposition or stabilization in soils still have to be and into soil microorganisms using the compound-specific 13C
identified. content of phospholipid fatty acids (Rubino et al., 2007; Kramer and
In our current study, we added two types of hydrothermally Gleixner, 2008). Moreover, changes in the13C content of various
synthesized biochar, a highly condensed, nitrogen free biochar pools enable the determination of mean residence times (Balesdent
expected to be stable in soil, and a nitrogen containing biochar and Mariotti, 1996; Gleixner et al., 2002). Consequently, the
with low condensation grade expected to be easily degradable, production of isotopically labeled biochars from simple isotopic
to different soils with the aim to answer the following precursors is most promising investigating synthetic biochars in
questions: the soil system. Biochars were produced by hydrothermal pyrolysis
(Titirici et al., 2007a,b) using glucose (signature G) and yeast
1) How stable are biochars produced by this method in different (signature Y) as parent material, respectively. A 13C label was
soils? introduced to both biochars adding uniformly 13C labeled glucose
2) How do inherited soil microorganisms react on the addition of (99 atom%, Sigma Aldrich, Seelze, Germany) to the parent materials
such biochars? prior to biochar synthesis.
3) Is the stability of these biochars tuneable by varying the Glucose should be seen as model compound for cellulose, the major
condensation grade and chemical composition of the biochar? structural component of plant biomass. Several investigations have
shown that charcoal produced from very different types of biomass
always show similar chemical structures (Schmidt and Noack, 2000;
2. Materials and methods Gleixner et al., 2001; Titirici et al., 2007b, in press). Heterocyclic (O-
containing) pyran and furan ring systems of carbohydrates or phenol
2.1. Soil sampling and characterization type structures that are the backbone of lignin form for example
benzene and other polyaromatic hydrocarbons (PAH) due to the
Soils used for the greenhouse experiment were sampled at the aromatization reactions in the charring process. Solid state 13C NMR
continued arable plot of the Jena Experiment (Roscher et al., 2004) examinations proof this remarkable structural and compositional
and at the old growth forest field site of the Hainich National Park similarity of all charcoals made from different sources of biomass
(Knohl et al., 2003), respectively. The soil of the Jena Experiment (Titirici et al., in press) and therefore we do not expect serious differ-
was classified as Eutric Fluvisol (FAO, 1998) and had a texture of 23% ences between charcoals produced from model compounds and from
clay, 64% silt and 13% sand (Kreutziger, personal communication). biomass (Baccile et al., submitted for publication).
The soil of the Hainich field site was a fertile Cambisol containing Yeast acted as a protein, i.e. nitrogen, rich model waste material
40% clay, 56% silt and 4% sand (Knohl et al., 2003). In September resulting from bioethanol, beer and wine production (pomace,
2007 the top 5 cm of soil were sampled at both field sites, passed draff, brewer grains, distiller’s grain or distiller’s wash (Belyea et al.,
through a sieve with a mesh size of 2 mm and partitioned for PLFA 1998; Pfeffer et al., 2007; Maas et al., 2008; Quintero et al., 2008))
extraction (fresh soil), for soil column filling and for chemical and thus represented a probable commercial source material for
analyses (dried at 40 C), respectively. the synthesis of nitrogen rich biochars. The yeast we used was
Soil carbon and nitrogen concentrations were measured from provided by a local beer brewery and represents the brewer grains
ball-milled sub-samples by elemental analysis (Elementar- that were separated from the beer product as described in the
analysator vario Max CN, Elementar Analysensysteme GmbH, literature above. The grains were basically made up of the yeast
Hanau, Germany) before and after incubation. Organic carbon active in the fermentation and additionally contain some rest of
concentration was determined by calculating the difference barley glume and wheat bran.
between elemental analyses of the total carbon concentration and Element composition and d13C values of the biochars were
soil inorganic carbon concentration (Steinbeiss et al., 2008b). For determined by elemental analysis and EA-IRMS as was described for
d13C analysis of the soil organic carbon, 3 mg ground sample was the soil samples, respectively (Table 1). Thermogravimetry
weighed in small tin capsules. The arable soil contained about 1.6% (TGA851e, Mettler-Toledo, Gießen, Germany) was applied to char-
inorganic carbon, which was removed by treatment with 120 ml of acterize the thermal stability and thus the carbonization grade of the
sulfurous acid (5–6% SO2, Merck, Darmstadt, Germany) prior to biochars (Meszaros et al., 2007; Pastor-Villegas et al., 2007; Strezov
isotope analysis (Steinbeiss et al., 2008a). Isotope ratios were et al., 2007). Samples, biochars and their respective parent materials,
measured by a coupling of an elemental analyzer (EA 1110) with an were introduced into the oven at 60 C and heated with a rate of
isotope ratio mass spectrometer (DeltaPlusXL, Thermo Finnigan, 1 C min1 to 850 C in an Argon atmosphere. Scanning electron
Bremen, Germany). All values represent repeated measurements microscopy (SEM) was performed on a DSM 940 A (Zeiss, Oberko-
with a standard deviation of less than 0.3& and were calibrated chen, Germany). Infrared-spectra were measured with an IFS 66 FTIR
versus V-PDB using CO2 as reference gas (Werner and Brand, 2001). spectrometer (Bruker Optik GmbH, Ettlingen, Germany). Spectra
Soil analyses were summarized in Table 1. were obtained averaging 128 scans, with a resolution of 4 cm1.
Table 1
Basic characterization of biochars and soils; sd refers to standard deviation of replicated measurements. For d13C values of CO2 gas in the controls the standard error of the
calculated y-intercept was given instead (see Methods section for details).
2.3. Experimental design and regular measurements type was extracted to leave the other two replicates for further
continuous measurements.
Soil columns were filled with 150 g soil (dry weight); 15 PLFA extraction was performed after standard methods
columns were filled with arable soil (signature A) and 15 columns described in the literature (Bligh and Dyer, 1959; Zelles and Bai,
were filled with forest soil (signature F). The soil of six columns of 1993). Briefly, soils were shaken for 2 h in a mixture of chloroform,
each soil type was mixed with glucose-derived biochar (signatures methanol and phosphate buffer. The lipid extracts (chloroform
AG and FG) and further six columns of each soil type were mixed phase) were transferred to silica-filled solid phase extraction
with yeast-derived biochar (signatures AY and FY). Three columns columns (SPE). Phospholipids were separated from neutral lipids
of each soil type were left as control without biochar (signatures A and glycolipids by eluting with chloroform, acetone and methanol,
and F). The amount of biochar added to the soil was calculated to respectively. The phospholipids in the methanol fraction were
correspond to a carbon addition of 30% of the initial soil organic hydrolyzed and methylated using a methanolic KOH solution
carbon content. Initial soil properties including PLFA analyses were leading to phospholipid fatty acid methyl esters.
determined from soil samples without incubation (signatures AI Quantification of the PLFAs per soil dry weight was performed
and FI) with triple replicates. on a GC-FID system (Agilent Technologies, Santa Clara, USA) using
Soil columns were incubated at 25 C during the day and 20 C a fused silica column (HP ultra 2, 50 m length 0.32 mm ID,
during the night. No artificial lighting was applied. Soil moisture 0.52 mm film thickness). The temperature program started at 140 C
was adjusted every three to four days in all columns. No water (1 min isotherm) followed by a heating rate of 2 C min1 to 270 C,
leached out from the columns. which was held for 9 min, and followed by a final heating rate of
Soil respiration was measured using a carbon dioxide probe 30 C min1 to 320 C. For peak identification retention times of
(GMP 343, Vaisala, Helsinki, Finland) from week 1 to week 25 with standard measurements were used.
a temporal resolution of 1 week in the beginning (up to week 7) and Compound-specific isotope ratios of the identified PLFAs were
2–3 weeks afterwards. The respired gas was collected in weeks 7, measured by GC–IRMS (DeltaPlusXL, Thermo Finnigan, Bremen,
12, 15, 17, 20, 23 and 26 using 2.3 l gas flasks connected via Germany). Gas chromatographic separation was performed with
a capillary to the soil columns (filling time 4 h per sample). Sample the same parameters as the quantification (see above). To obtain
air was dried chemically using magnesium perchlorate (Fisher d13C values of the PLFAs, measured isotope values were corrected
Scientific, Loughborough, UK). Each time two flasks were filled the for the methyl carbon added during methylation (Kramer and
same way with greenhouse air to correct ambient CO2 concentra- Gleixner, 2006).
tion and isotope ratios of the treatments (d13Ctreatment,korr) Identified PLFAs were assigned to certain microbial groups, i.e.
(Amundson et al., 1998). Gas CO2 concentration was measured by fungi (C18:2u6,9, C18:1u9), Gram-positive bacteria (branched
GC-FID (Agilent technologies, Santa Clara, USA) and stable carbon saturated fatty acids), Gram-negative bacteria (monounsaturated
isotope ratios were determined by isotope ratio mass spectrometry fatty acids) and bacteria in general (straight chain saturated fatty
(Finnigan MAT 252, Bremen, Germany). acids) (Zelles, 1997; Baath and Anderson, 2003; Waldrop and
Based on the isotopic difference between the respired CO2 from Firestone, 2004; Kramer and Gleixner, 2006; Allison et al., 2007).
biochars and from soil organic carbon it was possible to calculate
the proportion of biochar-derived carbon in the respired gas for 2.5. Statistical evaluation
every sampling date (Equation (1)) (Balesdent et al., 1998; Waldrop
and Firestone, 2004). To overcome possible treatment effects we Statistical evaluation of the data sets was performed with SPSS
determined the control values used in Equation (1) from the gas version 16.0 (SPSS Inc., Chicago, USA). For direct comparison of
measurements of the control treatments (A and F), assuming the treatments simple t-tests were used. To test for systematic effects of
same processes in the treatments as in the controls. We made the soil type, the charcoal type or any interaction of both variables
Keeling plots combining the measured d13C values for the complete in complete data sets of all treatments analyses of variance
time series of the gas collected from the respective control columns (ANOVA) were calculated. Principal component analyses using the
and the reciprocal CO2 concentration (1/CO2). The y-intercept of the proportion of microbial groups in the soil were performed to
linear fit (R2 ¼ 0.96 for A and R2 ¼ 0.97 for F) can be interpreted as compare the structure of the microbial community in the different
the d13C value of biologically produced CO2 during respiration treatments and the respective initial soil samples. Statistical
(Amundson et al., 1998) (Table 1). significance was assigned at the p 0.05 level.
reached the next maximum reaction rate at 325 C and showed 1.1
a last process similar to the glucose-derived biochar degradation
between 380 and 390 C. 1.0
Scanning electron microscopy (SEM) showed similar structures
0.9
of our model biochars (carbonaceous spheres and continuous
C-H aromatic
nanopore systems) as were observed for charcoals produced from 0.8
Absorbance
different biomass types (e.g. rice grains, oak leafs, pine needles) by
hydrothermal pyrolysis (Cui et al., 2006; Titirici et al., 2007b) 0.7 C-O-C
(Fig. 1). CH2, CH3 aliphatic
Infrared-spectra reveal a polar surface structure of the model 0.6 CH
biochars containing phenolic, carbonyl and hydroxyl functional aliphatic C=O
0.5 C=C aromatic
groups. The aromatic structure was more pronounced for the highly
condensed glucose-derived biochar, whereas the low condensation
0.4
grade of the yeast-derived biochar resulted in larger proportions of
saturated and unsaturated aliphatic structures (Fig. 2). Infrared- 0.3 OH
spectra of charcoals produced from biomass verify hydroxyl groups,
phenolic residues, carbonyl functions, aliphatic double bonds and 4500 4000 3500 3000 2500 2000 1500 1000 500 0
a certain degree of aromaticity as the typical biochar structure Wavenumber in cm-1
characteristics (Titirici et al., 2007b).
Fig. 2. Infrared-spectra of glucose-derived biochar (straight line) and yeast-derived
biochar (dashed line).
3.2. Soil respiration and gas measurements
Initial respiration rates differed strongly between the treat- the respired CO2. Two major differences were observed between
ments (Fig. 3) but did not correlate to the initial carbon content. the soil types. First, data variability as well between replicates as
In arable soil, both biochar treatments (AG, AY) showed similar between repeated samplings was much higher in arable soil
respiration rates to the control despite the carbon addition treatments than in forest soil treatments (p < 0.001). Second, the
(p ¼ 0.64 and 0.50, respectively). In forest soil, the highest initial proportion of biochar carbon in the respiration gas was generally
respiration was measured in the treatment with labile yeast- lower in forest soil treatments compared to arable soil treatments
derived biochar (FY), which was significantly higher (p < 0.001) (p ¼ 0.025). In detail, variability between replicates for arable soil
than both the control (F) and the treatment with glucose-derived treatments were 5.4% (AG) and 3.3% (AY) on average, while
biochar (FG). No difference was observed between the treatment standard deviations of 0.9% were observed for replicates of both
with stable glucose-derived biochar in forest soil and the forest soil treatments (FG and FY). The proportion of biochar-
respective control (p ¼ 1.00). Respiration rates strongly decreased derived carbon in the respiration gas was 28% (sd ¼ 7.9%) in the
within 4 weeks of incubation and had leveled off after 12 weeks AG treatment and 22% (sd ¼ 24.3%) in the AY treatment. In forest
to a constant median value of 2 mg C d1 for all treatments. No soil 8% (sd ¼ 1.2%) of the respired carbon derived from biochar in
systematic differences in respiration rates were observed between the FG treatment and 12% (sd ¼ 3.6%) derived from biochar in the
the treatments, although the FY treatment showed significantly FY treatment. In the AG treatment, the proportion of biochar-
higher respiration rates at some occasions within the first 10 derived CO2 showed an increasing trend with time, reaching the
weeks of the experiment (i.e. weeks 4 and 10: p < 0.001 and maximum of 43% in week 20. The AY treatment showed the most
p ¼ 0.062). inconsistent pattern in the composition of the respiration gas
Labeling with 13C led to isotopic differences of 24–31& during incubation, varying between 0 and 53% biochar carbon in
between biochar carbon and soil organic carbon (Table 1) which the gas without any regularity. In contrast, in the forest soil
was used to quantify the proportion of biochar-derived carbon in treatments the proportion of biochar carbon in the respiration gas
Fig. 1. SEM picture of (a) glucose-derived biochar and (b) yeast-derived biochar. Scale bar 10 mm.
S. Steinbeiss et al. / Soil Biology & Biochemistry 41 (2009) 1301–1310 1305
A F
60 AG 60 FG
AY FY
50 50
respiration rate in mg C d-1
40 40
30 30
20 20
10 10
0 0
0 5 10 15 20 25 0 5 10 15 20 25
week after experiment start week after experiment start
Fig. 3. Respiration rates for arable soil treatments (left) and forest soil treatments (right) including the respective controls during incubation. Error bars represent standard
deviations between three replicates per treatment.
was constant at 8% for FG, while FY showed a decreasing trend the treatments for better comparability (Fig. 4). Losses of soil
from 19% in week 7 down to 9% in week 17 and later on. organic carbon were generally smaller in the arable soil treat-
ments compared to the respective forest soil treatments and
biochar addition always increased the loss of carbon from the soil
3.3. Development of soil carbon stocks and mean residence times organic carbon pool (Table 4). In both soil types, soil organic
carbon losses were largest when labile yeast-derived biochar was
Measured respiration rates reflect temporary carbon losses and added (Fig. 4, Table 4). In these treatments, twice the amount of
varied over time due to temperature and soil moisture variability. soil organic carbon was respired compared to the controls.
The total carbon budget was thus determined by elemental analysis Moreover, yeast-derived biochar seemed to be better degradable
from soil sub-samples before and after four months of incubation than glucose-derived biochar as indicated by larger biochar
(Table 2). Total carbon content decreased in controls and all treat- carbon losses in both soil types (Fig. 4), although the difference
ments over the incubation time. Despite different absolute was significant only in forest soil (p ¼ 0.003, p ¼ 0.147 for arable
numbers in the carbon budget due to the different initial carbon soil). Most interestingly, normalized losses of soil and biochar
content of the two soil types, the relative amount of carbon carbon in the arable soil were almost identical (p ¼ 0.544), while
remaining in the soils after biochar incubation only depended on in forest soil less biochar carbon than soil organic carbon was lost
the type of biochar added but did not depend on the soil type itself (p < 0.001).
or any interaction between soil type and biochar type (Table 3). The mean residence times (Equation (2)) for biochar carbon
Thus, of the initially added 3% of charcoal carbon, both treatments were calculated from measured total carbon losses and the
with more stable glucose-derived biochar still contained 27% more proportions of biochar carbon in the respiration gas (Equation
carbon than the respective control, while both treatments with (1)). In total, the controls lost 4% (A) and 6% (F) of their initial
labile yeast-derived biochar still contained 23% more carbon than carbon content, treatments with glucose-derived biochar lost 7%
the respective control (Table 2). (AG) and 8% (FG) carbon, and addition of yeast-derived biochar
To quantify losses of biochar carbon and soil organic carbon caused total carbon losses of 10% (AY) and 11% (FY), respectively.
we used the isotopic signature of the respiration gas. We Consequently, mean residence times ranged between 4 (AG) and
normalized all losses to the respective initial carbon amounts of 29 (AY) years (Fig. 5). The 29 years were calculated for yeast-
derived biochar in arable soil and give just a rough estimate due
to the huge uncertainty caused by the high variability in the
Table 2
detected proportion of biochar carbon in the respiration gas.
Carbon budget in g C and relative to the respective controls for all treatments before
and after incubation; sd refers to standard deviation of replicated measurements.
treatment 90
A AG AY F FG FY
0 80
-8 50
-10
40
-12
-14 30
-16 20
-18
10
-20 soil organic carbon
-22 biochar carbon 0
AG AY FG FY
Fig. 4. Losses of biochar carbon and soil organic carbon after 4 months of incubation treatment
given relative to the respective initial amounts in the treatments. Error bars reflect the
uncertainties in the proportion of biochar carbon in the respiration gas used for Fig. 5. Calculated mean residence times for the biochars in the different treatments.
calculation and were determined according to error propagation laws. Error bars reflect the uncertainty caused by the variability of the proportion of biochar
carbon in the respiration gas. They were determined according to error propagation
laws.
18 18
AG FG
16 AY 16 FY
A F
isotopic shift in ‰ (treatment - inital) 14 14
12 12
10 10
8 8
6 6
4 4
2 2
0 0
fungi gram(+) gram(-) bacteria fungi gram(+) gram(-) bacteria
Fig. 7. Isotopic shift of PLFA biomarkers (treatment after incubation – initial values) for certain microbial groups, i.e. fungi, Gram-negative bacteria, Gram-positive bacteria and
bacteria in general. Error bars reflect the standard deviation in isotopic shift within a group of microorganisms.
biochars produced by hydrothermal pyrolysis would probably Inherited soil microorganisms adapted to the new carbon source
add to the decadal soil carbon pool. The fast decrease in soil and utilized both types of biochar. The biochar type determined,
respiration rates during incubation indicated that microbial which group of microorganisms were involved in the decomposi-
stimulation and thus decomposition processes remarkably tion process. Yeast-derived biochar strongly promoted fungi, while
slowed down after 4 months. Concluding from this observation, glucose-derived biochar primarily was utilized by Gram-negative
we assume that any fertilizer effect of these biochars will be bacteria.
biggest directly after biochar addition to the soils and that the
carbon storage function will gain importance on the longer term. 3) Is the stability of these biochars tuneable by varying the
Mean residence times given here represent results from the condensation grade and chemical composition of the
initial phase of biochar degradation and might increase with biochar?
time.
As has been shown for the total carbon stocks, also the Our results clearly show that the type of biochar, i.e. conden-
reaction of soil microorganisms on biochar addition was driven sation grade and chemical structure, is the main driver for all
by the biochar type and largely independent of the soil type. differences observed between our treatments. All patterns
Yeast-derived biochar strongly increased the proportion of fungi observed for the biochar types were the same in both soils. We thus
in both soils, which consequently turned out as the microbial conclude that the condensation grade and the chemical structure of
group that most utilized this type of biochar. Glucose-derived biochars produced by this method could serve as ‘‘tuning param-
biochar was used as carbon source for the build up of bacterial eter’’ to design biochars that act as fertilizers but simultaneously
biomass. Bacteria in arable soil, probably better adapted to add to the soil carbon pool on a decadal time scale.
carbon limitation events and more complex remaining soil In our current experiment we manipulated the condensation
carbon, respired more biochar carbon than bacteria in forest soil. grade and the nitrogen content of the biochars with promising
Consequently, calculated mean residence times of glucose- results. Several other elements (phosphorus, sulphur, cations)
derived biochar in arable soil were slightly shorter than in forest could be introduced to the biochar structure helping to fill special
soil. Microorganisms in the forest soil seemed to be less nutrient demands of arable lands. Further studies are necessary to
specialized on certain carbon sources. The adaptation of certain design the best possible soil amendments and to investigate the
microbial groups to biochar degradation was less pronounced long-term behavior of these biochars in natural systems.
than in arable soil.
To finally answer the questions that should be solved with our
experiment:
Acknowledgements
1) How stable are biochars produced by this method in different
soil? This investigation was financially supported by the Max Planck
Society within the scope of the EnerChem project house. We
Biochars produced by hydrothermal pyrolysis would add to the thank Maria M. Titirici for her help with SEM measurements at
decadal soil carbon pool. the Max Planck Institute of Colloids and Interfaces in Potsdam-
Golm. Valerian Ciobota and Petra Roesch kindly recorded the
2) How do inherited soil microorganisms react on the addition of Infrared-spectra at the Institute of Physical Chemistry of the
such biochars? Friedrich Schiller University in Jena.
S. Steinbeiss et al. / Soil Biology & Biochemistry 41 (2009) 1301–1310 1309
Appendix 1
Amounts of identified PLFAs in mg g1 soil dw and d13C values in & in initial soils, all treatments and the controls after incubation.
Standard deviations are given in parentheses. Source specific summaries can be found at the end of each section.
PLFA Source AI (mg g1 dw) AG (mg g1 dw) AY (mg g1 dw) A (mg g1 dw) FI (mg g1 dw) FG (mg g1 dw) FY (mg g1 dw) F (mg g1 dw)
C14:0 br Gram(þ) 1.8 (0.1) 0.4 (0.2) 0.7 (0.2) 2.5 5.1 (0.7) 2.5 (0.4) 2.3 (0.1) 2.1
C14:0 Bacteria 1.1 (0.1) 0.4 (0.1) 0.7 (0.1) 1.5 1.9 (0.2) 1.3 (0.2) 1.5 (0.1) 1.2
C15:1 Gram() 1.4 (0.1) 0.4 (0.2) 0.6 (0.1) 1.9 2.4 (0.2) 0.9 (0.1) 0.9 (0.0) 0.8
C15:0 br Gram(þ) 6.6 (0.6) 2.8 (1.2) 4.3 (0.7) 9.1 10.9 (0.9) 7.7 (1.2) 8.2 (0.4) 6.2
C15:0 br Gram(þ) 5.5 (0.5) 2.3 (0.9) 3.1 (0.5) 7.6 14.8 (1.0) 10.6 (1.7) 10.5 (0.6) 8.5
C15:0 Bacteria 0.6 (0.0) 0.4 (0.1) 0.6 (0.1) 0.8 0.8 (0.1) 0.7 (0.1) 0.7 (0.0) 0.5
C16:0 br Gram(þ) 0.6 (0.1) 0.4 (0.1) 0.4 (0.1) 0.8 0.9 (0.2) 0.9 (0.1) 0.7 (0.0) 0.7
C16:1 Gram() 1.2 (0.1) 0.5 (0.2) 0.6 (0.1) 1.7 1.8 (0.1) 1.0 (0.2) 0.9 (0.1) 0.8
C16:0 br Gram(þ) 3.6 (0.4) 1.8 (0.7) 2.1 (0.5) 5.1 5.4 (0.3) 4.2 (0.8) 4.2 (0.2) 3.1
C16:1 Gram() 2.4 (0.2) 1.1 (0.3) 1.7 (0.3) 3.4 4.2 (0.2) 1.7 (0.3) 2.0 (0.2) 1.5
C16:1 Gram() 10.6 (0.9) 4.6 (1.2) 5.6 (1.1) 14.6 11.8 (0.5) 4.9 (0.7) 5.6 (0.4) 4.8
C16:1 Gram() 6.0 (0.5) 3.1 (0.6) 3.4 (0.7) 8.3 8.5 (0.4) 3.1 (0.4) 3.2 (0.2) 2.8
C16:0 Bacteria 11.4 (1.2) 7.7 (1.5) 15.9 (3.3) 16.1 20.5 (0.9) 15.6 (2.4) 31.1 (2.9) 14.3
C17:0 br Gram(þ) 1.3 (0.1) 0.8 (0.2) 0.8 (0.1) 1.7 2.1 (0.1) 1.1 (0.1) 1.2 (0.1) 0.9
C17:1 Gram() 4.0 (0.4) 2.3 (0.6) 2.8 (0.6) 5.5 5.5 (0.3) 2.7 (0.4) 2.8 (0.2) 2.3
C17:0 br Gram(þ) 5.9 (0.5) 3.9 (0.7) 3.6 (0.9) 8.2 11.2 (0.5) 5.2 (0.9) 4.7 (0.3) 4.2
C17:0 br Gram(þ) 1.3 (0.1) 0.9 (0.1) 0.9 (0.1) 1.7 1.9 (0.1) 0.9 (0.1) 0.9 (0.1) 0.8
C17:0 br Gram(þ) 1.2 (0.1) 0.8 (0.1) 0.7 (0.2) 1.6 1.8 (0.1) 0.9 (0.1) 0.9 (0.0) 0.8
C17:0 br Gram(þ) 2.3 (0.2) 1.7 (0.4) 1.9 (0.3) 3.1 4.2 (0.2) 3.1 (0.5) 3.2 (0.2) 2.6
C17:0 br Gram(þ) 2.5 (0.2) 1.6 (0.3) 1.7 (0.4) 3.6 4.1 (0.2) 2.8 (0.4) 2.9 (0.2) 2.3
C17:1 Gram() 2.0 (0.2) 1.1 (0.3) 0.9 (0.2) 2.8 1.5 (0.1) 0.9 (0.1) 0.8 (0.0) 0.7
C17:1 Gram() 2.8 (0.2) 2.0 (0.3) 2.0 (0.4) 3.8 5.9 (0.2) 3.4 (0.5) 4.1 (0.3) 3.2
C17:0 Bacteria 0.5 (0.1) 0.4 (0.1) 0.5 (0.1) 0.7 0.7 (0.1) 0.7 (0.1) 0.7 (0.1) 0.5
C18:0 br Gram(þ) 2.3 (0.2) 1.8 (0.9) 1.7 (0.5) 3.2 3.0 (0.2) 2.7 (0.5) 2.4 (0.1) 1.9
C18:0 br Gram(þ) 0.5 (0.0) 0.3 (0.1) 0.3 (0.1) 0.6 0.7 (0.0) 0.4 (0.1) 0.4 (0.0) 0.3
C18:0 br Gram(þ) 1.0 (0.1) 0.8 (0.3) 0.7 (0.2) 1.5 1.4 (0.1) 1.5 (0.3) 1.2 (0.1) 1.0
C18:2u6,9 Fungi 3.4 (0.3) 1.6 (0.3) 15.9 (3.3) 4.7 3.5 (0.2) 1.8 (0.3) 27.3 (3.4) 1.5
C18:1u9 Fungi 13.5 (1.4) 7.4 (1.3) 22.0 (4.6) 19.0 25.7 (1.0) 15.5 (2.6) 39.7 (4.1) 13.6
C18:1u11 Gram() 21.2 (2.1) 14.1 (2.2) 16.6 (3.9) 29.3 46.7 (1.6) 26.2 (3.9) 31.1 (2.7) 23.2
C18:1 Gram() 1.8 (0.1) 1.2 (0.1) 1.4 (0.3) 2.8 2.9 (0.3) 1.3 (0.1) 1.7 (0.1) 1.2
C18:0 Bacteria 2.7 (0.3) 2.1 (0.4) 3.3 (0.8) 3.8 4.8 (0.3) 3.7 (0.6) 6.0 (0.5) 3.5
C18:0 cyc Gram() 1.7 (0.2) 1.3 (0.2) 1.6 (0.3) 2.3 3.2 (0.1) 3.0 (0.4) 3.7 (0.3) 2.8
C19:0 br Gram(þ) 2.6 (0.3) 1.8 (0.6) 2.3 (0.7) 3.6 4.8 (0.3) 4.0 (0.8) 4.6 (0.3) 2.9
C19:0 br Gram(þ) 0.7 (0.0) 0.6 (0.1) 0.5 (0.1) 1.1 1.3 (0.1) 1.0 (0.1) 1.0 (0.1) 0.7
C18:0 cyc Gram() 5.5 (0.6) 4.5 (0.5) 4.2 (1.0) 7.7 22.9 (0.9) 12.2 (2.0) 12.3 (0.9) 10.7
C20:1u9 Gram() 1.2 (0.1) 0.7 (0.2) 1.1 (0.2) 1.6 2.2 (0.2) 1.1 (0.2) 1.7 (0.2) 1.0
C20:0 Bacteria 0.7 (0.0) 0.4 (0.0) 0.6 (0.1) 0.9 1.0 (0.1) 0.8 (0.1) 1.1 (0.1) 0.8
Sum Gram() 61.8 36.9 42.5 85.7 119.5 62.4 70.8 55.8
Gram(þ) 39.7 22.7 25.7 55.0 73.5 49.5 48.3 39.0
Fungi 16.9 9.0 37.9 23.7 29.2 17.3 67.0 15.1
Bacteria 16.5 11.4 21.6 23.8 29.7 22.8 41.1 20.8
d13C (&) d13C (&) d13C (&) d13C (&) d13C (&) d13C (&) d13C (&) d13C (&)
C14:0 br Gram(þ) 29.4 (1.4) 26.6 (1.3) 29.4 (0.4) 28.5 (1.5) 30.6 (3.4) 28.1 (0.3)
C14:0 Bacteria 28.8 (0.3) 22.6 (0.5) 24.6 (1.3) 23.2 (0.9) 23.1 (0.9) 25.6 (1.2) 24.3 (0.0)
C15:1 Gram() 26.6 (2.1) 23.0 (0.6) 24.3 (0.5) 24.2 (0.3) 24.2 (0.2)
C15:0 br Gram(þ) 25.0 (0.6) 25.0 (1.1) 21.7 (0.2) 23.6 (1.4) 24.7 (0.3) 23.1 (1.0) 23.1 (1.2) 23.3 (0.5)
C15:0 br Gram(þ) 21.2 (0.2) 19.1 (1.2) 19.0 (0.3) 21.5 (0.7) 20.4 (0.2) 18.8 (0.2) 16.8 (0.6) 19.3 (0.3)
C15:0 Bacteria 27.8 (1.6) 23.0 (1.2) 25.9 (1.3) 25.7 (0.5) 26.0 (0.5)
C16:0 br Gram(þ) 22.5 (3.3) 22.8 (0.4) 25.3 (1.0) 28.0 (1.9) 24.3 (1.8) 26.4 (0.9)
C16:1 Gram() 27.1 (1.5) 21.4 (1.8) 24.5 (1.4) 26.3 (0.5)
C16:0 br Gram(þ) 25.2 (0.3) 23.7 (1.4) 22.5 (0.4) 25.9 (1.3) 23.8 (0.9) 25.5 (0.1)
C16:1 Gram() 21.3 (0.3) 19.0 (0.9) 17.1 (0.3) 20.8 (0.2) 23.4 (0.9) 20.3 (0.4) 19.5 (0.8) 20.2 (0.1)
C16:1 Gram() 26.1 (0.5) 20.5 (1.0) 21.6 (1.7) 24.9 (0.5) 25.9 (0.5) 22.4 (0.7) 21.3 (0.6) 25.1 (0.3)
C16:1 Gram() 20.7 (0.1) 18.8 (0.3) 18.7 (0.3) 21.3 (0.4) 21.5 (0.3) 18.6 (1.9) 17.4 (0.9) 20.2 (0.5)
C16:0 Bacteria 24.8 (1.4) 20.8 (0.8) 17.8 (1.0) 23.9 (0.5) 23.8 (0.1) 21.0 (1.1) 18.4 (0.2) 23.2 (0.2)
C17:0 br Gram(þ) 19.0 (1.1) 9.7 (0.8)
C17:1 Gram() 27.1 (1.0) 21.2 (0.6) 24.8 (1.5) 24.6 (0.4) 22.9 (1.6) 24.2 (1.7) 22.1 (0.5)
C17:0 br Gram(þ) 23.9 (0.3) 22.0 (0.2) 21.8 (0.9) 23.0 (0.5) 22.6 (0.4) 21.4 (1.1) 21.1 (1.1) 22.4 (0.6)
C17:0 br Gram(þ) 18.9 (0.7) 15.4 (0.7) 20.2 (0.0) 17.6 (1.7) 19.5 (1.3) 18.1 (0.1) 20.0 (1.3) 17.9 (1.3)
C17:0 br Gram(þ) 22.3 (0.3) 20.3 (0.6) 21.1 (1.1) 22.6 (0.2) 20.6 (1.4) 21.8 (1.3) 21.8 (0.4)
C17:0 br Gram(þ) 22.2 (0.3) 22.3 (0.6) 18.7 (0.4) 20.6 (0.4) 20.4 (0.2) 19.1 (1.1) 19.5 (0.7) 19.4 (0.5)
C17:1 Gram() 23.5 (0.6) 15.9 (1.3) 20.7 (0.6) 22.4 (0.7) 23.7 (0.3) 17.5 (1.7) 19.0 (0.4) 22.2 (0.5)
C17:0 Bacteria 24.4 (0.9) 20.6 (0.6) 22.0 (1.6) 16.6 (0.8) 19.4 (0.6) 21.0 (0.5)
C18:0 br Gram(þ) 25.5 (0.1) 24.2 (0.3) 24.0 (0.7) 26.1 (1.4) 24.3 (0.2) 22.3 (1.6) 22.7 (1.2) 23.9 (0.6)
C18:0 br Gram(þ) 21.6 (1.0) 24.0 (0.3) 20.5 (0.6)
C18:0 br Gram(þ) 27.3 (1.1) 23.9 (1.1) 26.6 (1.6) 22.9 (1.7) 17.0 (2.0) 23.6 (2.5) 20.7 (1.7)
C18:2u6,9 Fungi 31.6 (1.1) 31.0 (0.6) 15.4 (1.2) 29.7 (0.7) 28.0 (0.5) 19.6 (1.3) 18.6 (0.2) 23.2 (1.0)
C18:1u9 Fungi 27.1 (0.7) 24.6 (1.0) 13.8 (0.5) 27.2 (1.6) 23.3 (0.3) 22.2 (0.3) 13.8 (0.3) 22.7 (0.5)
C18:1u11 Gram() 24.8 (0.5) 16.7 (1.2) 17.6 (0.4) 24.7 (1.0) 24.6 (0.2) 19.5 (0.5) 18.2 (0.4) 23.3 (0.2)
(continued on next page)
1310 S. Steinbeiss et al. / Soil Biology & Biochemistry 41 (2009) 1301–1310
Appendix 1 (continued )
PLFA Source AI (mg g1 dw) AG (mg g1 dw) AY (mg g1 dw) A (mg g1 dw) FI (mg g1 dw) FG (mg g1 dw) FY (mg g1 dw) F (mg g1 dw)
C18:1 Gram() 14.9 (0.5) 10.1 (0.8) 13.0 (2.0) 15.2 (1.3) 14.5 (1.1) 8.2 (2.5) 5.5 (1.3) 10.8 (1.0)
C18:0 Bacteria 20.9 (0.7) 18.5 (0.3) 17.5 (0.3) 21.4 (1.2) 21.3 (0.5) 18.9 (0.5) 14.9 (0.3) 20.9 (0.4)
C18:0 cyc Gram() 21.1 (0.9) 16.6 (0.4) 19.4 (0.4) 20.5 (0.6) 23.7 (0.5) 16.9 (0.3) 15.3 (0.4) 21.9 (0.6)
C19:0 br Gram(þ) 29.1 (0.8) 23.3 (1.0) 25.8 (0.8) 22.1 (0.9) 21.7 (1.4) 18.7 (0.2) 21.7 (0.9)
C18:0 cyc Gram() 28.3 (0.5) 25.4 (1.0) 25.6 (1.2) 28.5 (0.8) 27.9 (0.4) 26.4 (0.4) 25.3 (0.5) 27.5 (0.3)
C20:0 Bacteria 21.6 (1.9) 23.6 (1.0) 25.4 (0.1) 20.9 (0.6) 21.5 (1.0)
Average Gram() 23.8 (4.0) 17.9 (4.4) 19.9 (3.3) 22.9 (3.4) 23.4 (3.5) 19.1 (5.1) 19.3 (6.2) 22.2 (4.4)
Gram(þ) 24.2 (3.1) 21.4 (3.3) 22.0 (2.4) 23.4 (2.9) 22.8 (3.2) 20.6 (4.3) 21.8 (3.8) 22.0 (3.5)
Fungi 29.4 (3.2) 27.8 (4.5) 14.6 (1.1) 28.5 (1.8) 25.7 (3.3) 20.9 (1.8) 16.2 (3.4) 23.0 (0.4)
Bacteria 25.3 (3.1) 19.7 (1.6) 20.5 (2.4) 24.0 (1.9) 23.3 (1.5) 21.0 (3.4) 19.8 (3.9) 22.8 (2.1)
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DOI 10.1007/s11104-007-9391-5
MARSCHNER REVIEW
Received: 19 April 2007 / Accepted: 9 August 2007 / Published online: 19 September 2007
# Springer Science + Business Media B.V. 2007
Abstract Experiments suggest that biomass-derived effects on mycorrhizal associations. After reviewing
black carbon (biochar) affects microbial populations the experimental evidence for such effects, we critically
and soil biogeochemistry. Both biochar and mycor- examine hypotheses pertaining to four mechanisms by
rhizal associations, ubiquitous symbioses in terrestrial which biochar could influence mycorrhizal abundance
ecosystems, are potentially important in various and/or functioning. These mechanisms are (in decreas-
ecosystem services provided by soils, contributing to ing order of currently available evidence supporting
sustainable plant production, ecosystem restoration, them): (a) alteration of soil physico-chemical proper-
and soil carbon sequestration and hence mitigation of ties; (b) indirect effects on mycorrhizae through effects
global climate change. As both biochar and mycor- on other soil microbes; (c) plant–fungus signaling
rhizal associations are subject to management, under- interference and detoxification of allelochemicals on
standing and exploiting interactions between them biochar; and (d) provision of refugia from fungal
could be advantageous. Here we focus on biochar grazers. We provide a roadmap for research aimed at
testing these mechanistic hypotheses.
Table 1 Effects of biochar (BC) or activated carbon/charcoal (AC) additions on mycorrhizal fungi, separated by mycorrhizal type (arbuscular mycorrhizal fungi (AMF)
ectomycorrhizal fungi (ECM), and ericoid mycorrhizal fungi (ERM), and listed in order of decreasing effect size of the mycorrhizal response variable(s)
Experimental designa Amouont ACb or BCb present Type(s) of BCc or ACc applied Response variablesd Mycorrhiza responsee Possible functions for Source
ECM, ERM or AMFf
AMF experiments
BC effects on AMF RC of BC: 800 g/m3 in 2, 4.8 m3 H: RH RC +610% ND Ishii and
Citrus iyo in an abandoned pits Kadoya
orchard (F) (1994)
Effects of three BC types on BC: 2.0% BW H: RH Citrus Juice RC +540% RH +88% Enhanced overall Ishii and
AMF (Glomus fasciculatum) Sediment (C.J.) C.J. +75% W.S. plant P nutrition Kadoya
in river sand (G) Woody: Western (1994)
Spruce Bark (W.S.)
BC Effects on AMF in soy bean BC: 1,500 g m−2 ND RC +300% ND Saito (1990)
fields (F)
BC (ground vs un-ground) BC: 33% BV H: RH RC Ground: +100% ND Ezawa et al.
effects on AMF infectivity (F) Un-ground: −20% (2002)
BC effects on AMF (Glomus sp.) BC : 10% and 30% BV Woody: Coconut Shell RC 10% BC: +50% 30% Enhanced plant Matsubara
and Fusarium oxysporum RC of BC: +69% pathogen resistance et al. (2002)
Asparagus officinalis roots. (G)
BC effects on infectivity of BC: Applied at a rate Woody: Acacia RC +42% ND Yamato et al.
indigenous AMF (G) of 10 l m−2 mangium bark (2006)
BC effects on AMF RC of non BC: Applied at rates of 0, Woody: Eucalyptus RC Non N-fixing: 30 g, ND Rondon et al.
N-fixing, and N-fixing 30, 60 and 90 g BC kg−1 soil deglupta logs 60 g: −38% 90 g: −20% (2007)
Phaseolus vulgaris) roots. (G) N-fixing: 30 g, 60 g:
NS; 90 g: +16%
BC Effects on AMF RC, and BC: 89.8% BV of ND RC SD in 100 ml−1 RC −21% SD: −5% ND Gaur and
Spore density (S.D.) by Glomus growth substrate infectious IP: −38% Adholeya
intraradices grown in culture propagules (IP) (2000)
with Zea mays (G) in 100 ml−1
ECM experiments
Quantified ECM RC in different BC: 2% BV ND RC, no. ECM +2,900% ND Harvey et al.
soil fractions of a Montana root tips 100 cm3 (1976)
forest soil (F) soil fraction −1
Effect of AC on timing of AC: 2% BW ND RC Onset of RC +624% Onset Colonization by P. Herrmann et
mycorrhizal colonization of mycorrhiza accelerated by croceum increased al. (2004)
Quercus robur seedlings formation 4 weeks drought resistance
by Piloderma croceum.(G) measured in weeks in Q. robur
AC effects on ability of ECM AC: 0.3% BV ND ECM presence or +200% ND Vaario et al.
(Pisolithus tinctorus) to absence of host (1999)
colonize Abies firma seedlings infection
Plant Soil (2007) 300:9–20
Experimental designa Amouont ACb or BCb present Type(s) of BCc or ACc applied Response variablesd Mycorrhiza responsee Possible functions for Source
ECM, ERM or AMFf
Effectiveness of RH BC/forest BC: 300 cm3 BC H: RH Presence or absence +80% ND Mori and
top soil mix as ECM inoculum mixed with 1 l soil. of host infection Marjenah
source for Shorea smithiana BC/soil mix placed in by ECM fungi (1994)
trees grown in degraded forest potting hole 25-cm deep×
soil. (F) 25-cm diameter
Effects of AC slurry on dissolved AC: Applied to soil as ND RC −38% in type ND Wellstedt
phenol concentration and Picea slurry, (250 g AC 3 l−1 B fungi et al. (2002)
mariana seedling growth (G) water) microcosm
Plant Soil (2007) 300:9–20
2004; Read et al. 2004; Rillig and Mummey 2006). Biochar definition and properties
Mycorrhizal fungi are frequently included in manage-
ment, since they are widely used as soil inoculum Biochar is a term reserved for the plant biomass-
additives (Schwartz et al. 2006). With both biochar derived materials contained within the black carbon
additions and mycorrhizal abundance subject to (BC) continuum. This definition includes chars and
management practices, there clearly are opportunities charcoal, and excludes fossil fuel products or geo-
for exploiting a potential synergism that could genic carbon (Lehmann et al. 2006). Materials
positively affect soil quality. forming the BC continuum are produced by partially
While data on biochar effects on mycorrhiza are combusting (charring) carbonaceous source materials,
accumulating, there are several important gaps in our e.g. plant tissues (Schmidt and Noack 2000; Preston
knowledge on these interactions. The most important and Schmidt 2006; Knicker 2007), and have both
gap concerns the mechanisms by which biochar might natural as well as anthropogenic sources. Restricting
affect the abundance and functioning of mycorrhizal the oxygen supply during combustion can prevent
fungi. Therefore, the goals of this paper are to first complete combustion (e.g., carbon volatilization and
evaluate the evidence of biochar effects on mycorrhi- ash production) of the source materials. When plant
zal associations thus far, and then to propose tissues are used as raw materials for biochar produc-
mechanisms for these biochar effects on mycorrhizae tion, heat produced during combustion volatilizes a
(primarily using examples of arbuscular mycorrhiza significant portion of the hydrogen and oxygen, along
and ectomycorrhiza). In doing so, we also point out with some of the carbon contained within the plant’s
future research priorities (Fig. 1). To clarify the tissues (Antal and Gronli 2003; Preston and Schmidt
nomenclature used throughout this discussion we first 2006). The remaining carbonaceous materials contain
provide a brief overview of biochar properties. many poly-aromatic (cyclic) hydrocarbons, some of
Fig. 1 Schematic representation of bio-char and its direct and through influences on other soil microbes; (3) interactions with
indirect effects on mycorrhizal fungi abundance/functioning, plant–fungus signaling; and (4) provision of refugia from
emphasizing the hierarchical nature of effects. The numbers fungal grazers. Solid arrows indicate direct facilitative effects;
included in figure body correspond to mechanisms discussed in dashed arrows indicate indirect facilitative effects
text: (1) effects on soil physio-chemical properties; (2) effects
Plant Soil (2007) 300:9–20 13
which may contain functional groups with oxygen or In three of the six ECM studies and the single
hydrogen (Schmidt and Noack 2000; Preston and ERM study represented in Table 1, experiments
Schmidt 2006). Depending on the temperatures demonstrated the effects of adding biochar in growth
reached during combustion and the species identity media on both the ability of the ECM and ERM fungi
of the source material, a biochar’s chemical and to colonize the host plant seedlings, and the overall
physical properties may vary (Keech et al. 2005; effects on seedling growth. Additionally, the experi-
Gundale and DeLuca 2006). For example, coniferous ment conducted by Herrmann et al. (2004) showed
biochars generated at lower temperatures, e.g. 350°C, that activated carbon (AC), which may in many cases
can contain larger amounts of available nutrients, have similar properties as biochar, affected the timing
while having a smaller sorptive capacity for cations of host plant colonization by ECMF, which occurred
than biochars generated at higher temperatures, e.g. 4 weeks earlier in the AC treatment than in the
800°C (Gundale and DeLuca 2006). Furthermore, control. The other ECM related experiments evaluated
plant species with many large diameter cells in their the effects of biochar presence on host tree coloniza-
stem tissues can lead to greater quantities of macro- tion rates (Harvey et al. 1976; Mori and Marjenah
pores in biochar particles. Larger numbers of macro- 1994). In these two cases, the presence of biochar
pores can for example enhance the ability of biochar corresponded with significant increases in plant root
to adsorb larger molecules such as phenolic com- colonization by ECM. Observations made by Harvey
pounds (Keech et al. 2005). et al. (1978, 1979) also support these results.
Because of its macromolecular structure dominated In contrast to those experiments in Table 1 showing
by aromatic C, biochar is more recalcitrant to positive effects of biochar or AC additions on
microbial decomposition than uncharred organic abundance of mycorrhizal fungi, a few studies
matter (Baldock and Smernik, 2002). Biochar is observed negative effects. In these cases, it appears
believed to have long mean residence times in soil, that the negative effects of the biochar or AC additions
ranging from 1,000 to 10,000 years, with 5,000 years on AMF were largely due to nutrient effects. For
being a common estimate (Skjemstad et al. 1998; example, Gaur and Adholeya (2000) found that the
Swift 2001; Krull et al. 2003). However, its recalci- biochar media limited the amount of P taken up by
trance and physical nature represent significant host plants, compared to rates from plants grown in
obstacles to the quantification of long-term stability river sand or clay-brick granules, suggesting that P
(Lehmann 2007). was less available. Additionally, Wallstedt et al. (2002)
reported decreases in both bio-available organic
carbon and nitrogen in their ectomycorrhizal system.
Evidence for biochar effects on mycorrhizal fungi An important consideration pertains to the study
design of the experiments reported in Table 1. The
From the experiments summarized in Table 1, it first issue deals with the soils used in the experiments,
appears that the addition of biochar materials to soil e.g. river sand or OM-rich field soil; the other issue
often results in significant responses by both plants concerns the materials added to these soils as controls,
and mycorrhizal fungi. e.g. organic matter vs biochar. Are soil biota,
Tryon (1948), Matsubara et al. (2002), DeLuca et including mycorrhizal fungi, responding to an exper-
al. (2006), and Gundale and DeLuca (2006) demon- imental addition of biochar simply because carbon is
strated that biochar additions can change soil nutrient being added or are they responding to biochar’s
availability by affecting soil physico-chemical prop- unique properties? In at least two cases where data
erties. Increases in soil nutrient availability may result from field soils were presented, it appears that
in enhanced host plant performance and elevated mycorrhizal fungi responded more positively to
tissue nutrient concentrations in addition to higher biochar additions than to additions of other types of
colonization rates of the host plant roots by AMF organic material added as control (Harvey et al. 1976;
(Ishii and Kadoya 1994). Lastly, experiments by Ishii and Kadoya 1994). The experiment by Matsubara
Matsubara et al. (2002) suggested that biochar can et al. (2002) showed that a fresh organic amendment
also increase the ability of AMF to assist their host in had fairly similar effects as biochar in increasing AMF-
resisting infection by plant pathogens. mediated host plant resistance against Fusarium and
14 Plant Soil (2007) 300:9–20
that the asparagus plants reached similar mycorrhizal of this discussion is identifying mechanisms explain-
colonization levels with both additions. But the 9-week ing the effects of biochar on mycorrhizae, with the
gap between inoculation with AMF and with Fusarium intention of guiding attempts for developing methods
makes this aspect of the experiment somewhat difficult to exploit them as soil management tools, and because
to evaluate. However, it is still possible that these many of the biochar effects included in Table 1 appear
positive responses shown by mycorrhizal fungi are positive, we primarily present arguments explaining why
determined in part by the amount of carbon in the biochar generally appears beneficial to mycorrhizae.
material being added to the soil, with the expectation However, as discussed previously, biochar appli-
that the biochar is more carbon-rich than the organic cations do not always benefit mycorrhizal fungi (see
matter. We may not be able to answer this question Table 1). In these situations, one could argue that
satisfactorily until experiments control for C amend- biochar, via any of our proposed mechanisms, reduces
ment effects in the biochar treatment(s) and/or take into formation of mycorrhiza, e.g. by decreasing nutrient
account the relative addition of C to soils. availability or creating unfavourable nutrient ratios in
Work on terra preta de índio (TP) soil, the fertile soils (Wallstedt et al. 2002). This negative effect
Amazonian Dark Earths, has served as a major could be especially prominent in cases where the
inspiration for the use of biochar as a promising soil biochar has a very high C/N ratio and a portion of the
additive promoting crop growth and carbon storage biochar is decomposable, leading to N-immobiliza-
(Glaser et al. 2002; Glaser and Woods 2004; tion. Under such conditions, biochar could also
Lehmann et al. 2006; Glaser 2007). However, no negatively affect plant growth, e.g. as seen in Gaur
published data are available on the impact of TP soils and Adholeya (2000). Given the above possibilities
on mycorrhizal functioning. For that reason, the for negative responses by both plants and mycorrhizal
studies discussed above refer to short-term experi- fungi to biochar amendments, and plants to mycor-
ments and not to the historical, pre-Columbian rhizal fungi (Johnson 1993), it cannot be assumed that
Amazonian soils. TP soils are not only much richer biochar amendments will always result in a net
in biochar than the surrounding soils, but also in non- benefit to plant productivity even though few such
pyrogenic carbon and nutrients, especially phospho- cases have been reported so far.
rus and calcium; therefore it is likely that TP effects A conceptual overview of the mechanisms and
on mycorrhizal functioning could be beyond those of hypothesized pathways discussed in the following
biochar addition alone. sections is provided in Fig. 1, emphasizing the
hierarchical nature of contributing factors. In the
following discussion it should be kept in mind that
(a) mechanisms are not mutually exclusive but likely
Mechanisms several contribute to the outcome, perhaps even with
opposite effects; (b) there is little information avail-
At least four mechanisms could explain how biochar able on which mechanism is likely the most important
can lead to altered total abundance and/or activity of in any given environmental situation; and finally that
mycorrhizal fungi in soils and plant roots: (1) Biochar (c) many mechanisms are hypothetical with most
additions to soil result in altered levels of nutrient support for mechanism 1 at this time (we are
availability and/or other alterations in soil physico- presenting mechanisms below in decreasing amount
chemical parameters that have effects on both plants of evidence). This figure therefore also serves as a
and mycorrhizal fungi. (2) Additions of biochar to roadmap for future research.
soils result in alterations with effects that are
beneficial or detrimental to other soil microbes, for Mechanism 1: Biochar changes soil nutrient
instance mycorrhization helper bacteria (MHB) or availability
phosphate solubilizing bacteria (PBS). (3) Biochar in
soils alters plant–mycorrhizal fungi signaling process- Modifications of nutrient availability would clearly be
es or detoxifies allelochemicals leading to altered root a mechanism of primary importance for mycorrhizal
colonization by mycorrhizal fungi. (4) Biochar serves fungal abundance. For example, nutrient additions
as a refuge from hyphal grazers. Since a primary goal might alleviate growth limitations of the fungi
Plant Soil (2007) 300:9–20 15
themselves in nutrient-poor soils (Treseder and Allen 1994; Matsubara et al. 2002; Yamato et al. 2006). In a
2002). Additionally, altering the balance of nutrients greenhouse experiment by Matsubara et al. (2002),
can exert strong control over fungal root colonization, the soil pH of treatments receiving biochar increased
as for example known for shifts in soil N/P ratios for from 5.4 to 6.2 (10% biochar by volume) and 6.3
AMF (Miller et al. 2002). (30% biochar by volume). According to Lucas and
Biochar addition can result in elevated quantities of Davis (1961), these pH values fall within the pH
bio-available nutrients such as N, P and metal ions, in range (5.5 to 7.0) where plant nutrients are near their
the affected soils (Tryon 1948; Lehmann et al. 2003; maximum availability in agricultural soils. Many of
Gundale and DeLuca 2006; DeLuca et al. 2006), but these alterations in soil characteristics probably occur
has also been shown to lead to decreases particularly at a micro-scale (Gundale and DeLuca 2006), and thus
of N availability (Lehmann et al. 2003). These may only affect hyphae that are in the immediate
changes in soil nutrient availabilities, may be vicinity of biochar particles.
explained by some of the following observations.
Additions of biochar to soil alters important soil Mechanism 2: Biochar alters the activity of other
chemical and physical (see below) properties such as micro-organisms that have effects on mycorrhizae
pH (has caused both increases and decreases), and
typically increase soil cation exchange capacity Mycorrhization Helper Bacteria (MHB; Garbaye 1994)
(CEC), and can lead to greater water holding capacity are capable, under specific conditions, of secreting
(WHC), while generally decreasing bulk density metabolites, e.g. flavonoids (AMF) and furans (ECM),
(Tryon 1948). Increases in soil pH towards neutral that facilitate the growth of fungal hyphae and the
values (Lucas and Davis 1961), in addition to subsequent colonization of plant roots by ECM
increased CEC (Glaser et al. 2002), may result in (Founoune et al. 2002; Duponnois and Plenchette
increases in bio-available P and base cations in 2003; Aspray et al. 2006; Riedlinger et al. 2006) and
biochar influenced soils. Additionally, Lehmann et AM fungi (Duponnois and Plenchette 2003; Hildebrandt
al. (2003), Topoliantz et al. (2005), Gundale and et al. 2002, 2006). Hildebrandt et al. (2002, 2006) have
DeLuca (2006) and Yamato et al. (2006) showed that demonstrated that certain compounds (including raffi-
biochar itself contained small amounts of nutrients nose and other unidentified metabolites) produced by
that would be available to both soil biota (including strains of Paenibacillus can directly enhance the
mycorrhizal fungi) and plant roots. Lastly, DeLuca et growth of AMF extraradical mycelium. Additionally,
al. (2006) showed that biochar from forest wildfire Kothamasi et al. (2006) demonstrated that other species
stimulated gross and net nitrification rates, most likely of bacteria, such as Pseudomonas aeruginosa, can
mediated by biochar adsorbing inhibitory phenols. solubilize important plant nutrients, especially phos-
This mechanism is likely specific to soils with phate, making them part of a group of bacteria called
ectomycorrhizal trees and/or ericaceous shrubs with phosphate solubilizing bacteria (PSB). These mineral-
an abundance of phenolic compounds, whereas in ized nutrients are then accessible to mycorrhizal fungi
agricultural soils biochar may in the short term reduce and eventually to the host plant. Furthermore, Xie et al.
ammonification and nitrification by a reduction either (1995) and Cohn et al. (1998) state that Rhizobium sp.
in N availability due to immobilization during initial and Bradyrhizobium sp. can produce compounds that
decomposition of the N-poor biochar (Lehmann et al. induce flavonoid production in nearby plants (legumes)
2006) or by a reduction in C cycling. that may ultimately increase root colonization of plant
Some of the experiments conducted to evaluate roots by AM fungi.
the effects of biochar upon mycorrhizae (Table 1) Biochar may serve as a source of reduced carbon
lend support to mechanism 1. These experiments compounds (either the biochar particle itself, or organic
show that additions of biochar materials generally molecules adsorbed to the particle’s matrix), and/or
result in the alteration of soil physico-chemical nutrients, and as a refuge (see mechanism 4) for any
properties that may lead to increases in soil nutrient biochar colonizing soil bacteria, including MHB and
availability (measurements taken from both soil PSBs (Pietikäinen et al. 2000; Samonin and Elikova
samples and plant tissues) and/or increases in root 2004). Increased populations of PSB and/or MHB
colonization by mycorrhizal fungi (Ishii and Kadoya might then indirectly benefit mycorrhizal fungi (Fig. 1).
16 Plant Soil (2007) 300:9–20
Mechanism 3: Biochar alters the signaling dynamics sources of signal molecules, acting concomitantly
between plants and mycorrhizal fungi or detoxifies with MHB and plant roots.
allelochemicals However, biochar’s capacity to adsorb signaling
compounds and add as a sink could also decrease the
The rhizosphere is a zone of intense signaling ability of mycorrhizal fungi to colonize plant roots. If
between microbes, including mycorrhizal fungi, and biochar permanently rather than temporarily removes
plant roots (Bais et al. 2004; Harrison 2005; Bais et signal molecules from soils, this signal sorption
al. 2006; Paszkowski 2006). For example, experiments activity results in a net decrease in the number of
conducted using both field soils and in vitro cultures signal molecules reaching mycorrhizal hyphae and
show that compounds (e.g. CO2, flavonoids, sesquiter- spores. As a result, hyphal growth and spore germina-
penes and strigolactones) secreted by plant roots lead to tion, and ultimately fungal abundance, could actually
both increased colonization of plant roots by AMF decrease because of biochar activity.
(Bécard and Piché 1989; Nair et al. 1991; Xie et al. In addition to chemical signals, biochar may also
1995) and increased spore germination and AMF hyphal adsorb compounds toxic to mycorrhizal fungi. For
branching (Gianinazzi-Pearson et al. 1989; Akiyama et example, Wallstedt et al. (2002) showed that the
al. 2005). Additions of biochar could alter the exchange addition of an AC slurry to an experimental soil
of signals in several ways, as shown in Fig. 1; however, resulted in a decreased amount of water-soluble
we emphasize that most of the pertinent evidence stems phenols. Herrmann et al. (2004) and Vaario et al.
from sterile in vitro culture studies with uncertain (1999) related their results of stimulated ECM fungus
relevance to conditions in the soil. colonization of roots in the presence of AC to toxin
Angelini et al. (2003) demonstrated that some sorption.
flavonoid signaling compounds could be either
inhibitory or stimulatory to specific groups of soil Mechanism 4: Biochar serves as a refuge
biota as a function of pH. As discussed under for colonizing fungi and bacteria
mechanism 1, biochar additions usually increase soil
pH. Hence, it is possible that these pH changes alone This mechanism is purely physical in nature, and
can lead to stimulatory effects, causing increases in therefore could function in a similar fashion for ECM,
fungal abundance. ERM, AMF and bacteria. Hyphae and bacteria that
Sorptive properties of biochar (e.g. for hydropho- colonize biochar particles (or other porous materials)
bic substances), particularly higher temperature (e.g., may be protected from soil predators (Saito 1990;
800°C) biochar, could also cause signaling interfer- Pietikäinen et al. 2000; Ezawa et al. 2002), which
ence in the rhizosphere: biochar could serve as signal includes mites, collembola and larger (>16 μm in
reservoirs or as a sink, both for signaling compounds diameter) protozoans and nematodes. The docu-
and for inhibitory compounds (allelochemicals). Re- mented physical parameters of the biochar particles
cently, Akiyama et al. (2005) demonstrated that AC themselves make this mechanism plausible. The
was capable of adsorbing AMF signaling (strigolac- average sizes of soil bacteria and fungal hyphae range
tones) compounds from a hydroponic solution that from 1 to 4 μm and 2 to 64 μm, respectively, with
were subsequently desorbable with acetone. Once many fungal hypha being smaller than 16 μm in
desorbed, these compounds retained their activity and diameter (Swift et al. 1979). Additionally, the average
stimulate hyphal branching and growth of Gigaspora body-size of a soil protist is between 8 to 100 μm,
margarita. Biochar particles could adsorb signal while the average body size of soil micro-arthropods
molecules not immediately intercepted by AMF ranges from 100 μm to 2 mm (Swift et al. 1979). In
hyphae or spores, or consumed by other soil biota. contrast, the pore diameters in a biochar particle can
Later on, these stored signal molecules could be often be smaller than 16 μm in diameter (Kawamoto
desorbed by soil water reaching the biochar particles. et al. 2005; Glaser 2007; Hockaday et al. 2007).
After being re-dissolved into soil water, they would Based on the differences in the body sizes across
again be available to stimulate mycorrhizal coloniza- these different organisms, it is clearly possible that
tion of plant roots. By functioning in this manner, many of the pores within a biochar particle are large
biochar particles would be serving as secondary enough to accommodate soil microorganisms, includ-
Plant Soil (2007) 300:9–20 17
ing most bacteria and many fungi, to the exclusion of gy with arbuscular, ericoid, and ectomycorrhizal
their larger predators. Thus, the biochar would be symbioses. We have synthesized available data into
acting as a refuge for MHB, PSB and mycorrhizal several potential mechanisms of biochar effects on
fungi. Supporting evidence for this hypothesis comes mycorrhizae (Fig. 1). This should serve as a spring-
from Saito (1990), Gaur and Adholeya (2000) and board for testing the occurrence and relative impor-
Ezawa et al. (2002) who all showed that AMF readily tance of these factors/mechanisms in the soil. Based
colonize porous materials and were capable of heavily on this discussion we derive the following research
colonizing biochar particles in the soil. Lastly, recommendations:
Pietikäinen et al. (2000) and Samonin and Elikova
(2004) showed that bacteria readily colonized biochar (a) Methods reporting. In many cases it is helpful to
particles; these may include MHB and/or PSB. know as much detail about the experimental
An important factor controlling pore size distribution biochar application as possible. This should in-
is the charring temperature with higher temperatures clude: source material, production temperature,
yielding finer pores. Another major factor in determining application rate, application method, and what
the degree to which biochar may serve as a refuge is the material was used in the control application to
anatomical structure of the biological tissues pyrolyzed account for C addition effects (and the amounts of
to yield the biochar. Considering the effects that cell available nutrients for both). This would facilitate
diameter alone can have on the sorptive capability of a comparisons among studies and help distinguish
given biochar material (Keech et al. 2005; Gundale and among the different mechanistic pathways; fre-
DeLuca 2006), it stands to reason that the cell types quently these pieces of information are incomplete.
contained within the original plant tissues (e.g., (b) Management implications. None of the studies to
tracheids, vessel elements or sieve cells) determine the date have examined the management context of
pore sizes of the biochar. Not only the charring biochar application on AMF, and this would also be
conditions and source material, but also subsequent an important research need, since application
interactions of biochar with soil can change porosity practices could have overriding effects on soil biota.
and pore sizes. For example, adsorption of organic (c) Fungal communities. Studies to date have focused
matter to biochar surfaces can decrease porosity by on quantifying potential responses in fungal abun-
blocking pores (Kwon and Pignatello 2005). dance measures, primarily root colonization and
While it seems clear that mycorrhizal fungi can use spore numbers (see Table 1). However, mycorrhi-
biochar as a habitat, the quantitative importance to the zal fungi occur as species assemblages in ecosys-
extraradical mycelium is not evident. This will highly tems and in roots of individual plants (Johnson et
depend on the biochar properties and the biochar al. 1992; Husband et al. 2002; Vandenkoornhuyse
addition rates. Nevertheless, the finer parts of the et al. 2003; Mummey et al. 2005). The species
mycelium, generally the absorptive hyphae, are more composition of a mycorrhizal fungal assemblage
vulnerable to fungal grazers (Klironomos and Kendrick can be important to mycorrhizal functioning (e.g.,
1996), and it is primarily these architectural elements van der Heijden et al. 1998). Data on this
that could be effectively protected within biochar important aspect of the response of mycorrhizal
particles. It would depend, then, on the extent to which fungi to biochar are not yet available, but represent
these ‘protected’ fine hyphae make a substantial an important priority for future studies. Here, we
contribution towards nutrient uptake compared to the limited our discussion to mechanisms affecting
relatively ‘unprotected’ hyphae in the mineral and abundance; however, many of the arguments
organic soil, whether this hypothesized mechanism is presented could also be applied to explain poten-
quantitatively important. tial shifts in mycorrhizal fungal species composi-
tion, because fungal life history strategies and
responsiveness to changing soil environments vary
Conclusions and research recommendations between fungal taxa (e.g., Hart and Reader 2002;
Escudero and Mendoza 2005; Drew et al. 2006).
Experimental results (Table 1) point to exciting (d) Negative effects. There is a potential for negative
possibilities regarding biochar and its possible syner- effects on mycorrhizal fungi, as discussed above;
18 Plant Soil (2007) 300:9–20
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Impact of Biological Growths
(personal communication D. Day 2005)
- Glomalin lifespans averages 24 years, carbon in aggregates can be shorter but still ~18 years. (300x the
life of the fungi
With ~32% of SOC =carbon in aggregates resulting from glomalin, = ~480Gt (Nichols)
- An amount directly tied to AM Fungi and glomalin growth = ~31Gt of the carbon from glomalin and
carbon resulting from glomalin (CRFG), classed as in the annual pool of flux.
- CFG/CRFG probably does not rise linearly with glomalin growth but probably does increase as 50% of the
total increase in AM fungi rise.
- There are 93.5M km2 of biologically active land (UNEP) then ~334ton km-1 yr-1 of CFG/CRFG are in
annual flux.
- No till studies in the U.S. have found that soil carbon increases (mid level results) at 163 ton km-1 yr-1.
- Assuming charcoal addition can provide a 200% increase in AM fungi growth (Low end of Ishii's findings)
- If 33% of the land were dedicated to energy crops and and converted to hydrogen or other fuel (7% yield
@ ~2.5x107j kg-1), replacing coal (5.8x106j kg-1), and would replace 219 ton C km-1 of fossil C with C
from bio-energy production.
- Then 2.2 x10E6 km2 (2.0% of the earth's biologically active land) would need to be treated once every 3
yrs with a ton per hector with low temp char (or equivalent nutient enhanced charcaol) and using notill
farming to create a sink to offset the 1.7Gt buildup.
- A 400% AM fungi increase, then we would need to treat 1.5x10E6 km2 (1.6% of the earth biologically
active land or 2.8 times the size of France). It is possible these amounts are not required annually since
there is a significant carry over benefit from year to year. Ogawa (Japan) recommends only once every
three years.
Environ Sci Pollut Res (2009) 16:1–9
DOI 10.1007/s11356-008-0041-0
Received: 28 December 2007 / Accepted: 10 August 2008 / Published online: 27 August 2008
# Springer-Verlag 2008
sludge (Sigua et al. 2005; Su et al. 2007). However, the fertilizers or conditioners to increase crop yield and plant
presence of potentially toxic chemicals such as heavy growth by supplying and retaining nutrients (Glaser et al.
metals in sludge could pose risks to the environment and 2000; Major et al. 2005; Steiner et al. 2007). However,
human health (Illera et al. 2000; Hseu 2006). Composting is there has been no research to date on the potential
regarded as an effective treatment process to suppress application of bamboo charcoal in nutrient conservation
pathogenic organisms and stabilize the organic material in and heavy metal stabilization during sludge composting.
sewage sludge (Fang and Wong 1999; Hernández et al. The main objectives of this study, therefore, are to
2006). However, the stabilization effect of composting on investigate the potential capability of BC to stabilize heavy
heavy metal mobility in sludge has been shown to be very metals and retain nitrogen during sludge composting and to
limited (Amir et al. 2005; Liu et al. 2007). On the other clarify the possible mechanisms related to these functions.
hand, nutrient loss is an unavoidable problem during the We assume that the results of this study will provide
composting of organic waste. This is especially the case for practical information to guide the exploitation of a novel
nitrogen, the most essential fertilizer nutrient for crop compost amendment in agricultural applications.
production in many situations (Cooperband and Middleton
1996; Rao Bhamidimarri and Pandey 1996). According to
previous research, total nitrogen (TN) loss during the course 2 Materials and methods
of composting organic waste ranged from 16% to 76%
(Barrington et al. 2002; Raviv et al. 2002). Substantial loss The sewage sludge was collected from Fuyang wastewater
of nitrogen results in the reduction of nutrient value of treatment plant located in a suburb of Hangzhou city,
compost products. Among all practicable nitrogen conserva- China. It treats more than 100,000 m3 of wastewater
tion measures, an amendment was thought to be the most annually and produces about 90 tons day−1 of sludge
efficient method to reduce nitrogen loss during composting. (80% water content). The bamboo charcoal particles used in
For example, alum, peat, and zeolite amendments have been this study were purchased from the Yaoshi Charcoal-
used to reduce ammonia volatilization during composting Production Company located in Hangzhou. Rapeseed marc
(Bernal et al. 1993; Kithome et al. 1999). Lime and coal fly was purchased from a local farm, which was used as a
ash have also been applied as amendments to reduce the bulking agent in sludge composting due to its higher bulk
mobility of heavy metals in composting mixtures (Fang and density and lower moisture content. Characteristics of
Wong 1999; Qiao and Ho 1997). Nevertheless, low sludge, bamboo charcoal, and rapeseed marc are listed in
efficiency, potentially negative influence on soil pH, and Table 1. Cu and Zn were chosen as sludge metals for study,
high cost are factors that have prevented these amendments because they are quantitatively prevalent metals in sludges
from being adopted broadly in composting technology. and are known to have higher bioavailability than less
Bamboo charcoal (BC) is one kind of manufactured soluble metals such as Pb and Cr according to previous
biocharcoal, a plentiful residual byproduct of the bamboo studies (Oliveira et al. 2007; Dai et al. 2007).
processing industry. BC has a highly microporous physical
structure. The porosity is about five times greater and the 2.1 Composting and sampling
absorption efficiency ten times higher than that of wood
charcoal (Zhang 2001). Bamboo charcoal may be an ideal Composting was carried out in a tank with dimensions of
amendment for nutrient conservation and heavy metal 1.0×0.4×1.0 m and a volume of approximately 0.4 m3.
stabilization due to its excellent adsorption capability. There were six different treatments. The stock material
Recent research found that biocharcoals could act as soil consisted of 180-kg sewage sludge and 20-kg rapeseed
Total nitrogen (%) 2.31±0.15 Total nitrogen (%) 1.01±0.05 Pyrolysis temperature (°C) 600
Organic matter (%) 34.32±2.26 Organic matter (%) 73.62±4.22 Density (g cm−3) 0.75±0.04
Total phosphorus (%) 1.5±0.10 Total phosphorus (%) 0.45±0.02 Specific surface (m2 g−1) 330±24
pH 7.41±0.15 pH 8.23±3.55 pH 7.32±0.1
Water content (%) 78.72±2.2 Water content (%) 8.30±4.24 Water content (%) 10±1
Total Zn (mg kg−1) 1,530±56 Total Zn (mg kg−1) ND Total Zn (mg kg−1) 0.45±0.03
Total Cu (mg kg−1) 270±15 Total Cu (mg kg−1) ND Total Cu (mg kg−1) ND
C/N 16±1 C/N 129±5 C/N 356±10
ND No detection
Environ Sci Pollut Res (2009) 16:1–9 3
marc with 0%, 1%, 3%, 5%, 7%, 9% (w/w) of BC were used as stock chemicals in the BC adsorption
incorporated into the stock material. These BC treatments experiments and the concentrations were dependent on the
are labeled as control, 1% BC, 3% BC, 5% BC, 7% BC, actual concentration in sludge of these ions. The solutions
and 9% BC. Aeration was ensured by forced ventilation with BC particle were then kept in a thermostatic shaker at
during the first 3 weeks of composting and by turning the 250 rpm and 25°C for 48 h to achieve equilibrium.
pile over manually during the remaining incubation time. Afterwards, each sample was filtered to separate the FBC/
Temperature of the composting pile was recorded daily CBC particles from solution. These particles were analyzed
using temperature sensors. Each sampling was carried out to determine amounts of Cu Zn and ammonium adsorbed
in triplicate. All together, six times of samplings were and used for desorption tests. For the desorption experi-
performed. ment, the residual FBC or CBC samples collected from the
adsorption experiment were extracted by 0.05 M DTPA
2.2 Chemical analyses solution to measure the strength of Cu2+ and Zn2+ retention
on FBC/CBC. The detection process was the same as
Total nitrogen was measured by the Kjeldahl digestion described in the adsorption experiment. The heavy metal
method (Hernández et al. 2006). Total organic matter was retention capability was expressed as the percent of the total
determined by potassium dichromate (K2Cr2O7) and sulfu- Cu and Zn in BC that was retained after extracting by
ric acid (H2SO4) oxidation (Dai et al. 2007). Pile mass was DTPA. The FBC/CBC particles which had already reached
based on the total mass of all the composting material ammonium adsorption equilibrium were extracted with
including sludge, bamboo charcoal, and rapeseed marc at 30 mL of 0.01 M CaCl2 (Nishantha Fernando et al. 2005)
the initial and the final composting stages. Based on the N using the same conditions as described for adsorption. The
concentration and the total pile mass before and after ammonium retention capability was expressed by the same
composting, the actual N loss could be obtained. The actual approach described for metals. In the adsorption–desorption
N amount was calculated by multiplying the N concentra- test, triplicated sampling were implemented for the analysis
tion and the total pile mass of the composting material. The of the bamboo charcoal in initial composting material and
actual N loss was the difference between the initial N final composting material.
amount and the final N amount in the composting materials.
Boehm titration (Boehm 1994) was used to quantify 2.4 Data analysis
various surface functional groups on the fresh BC (FBC)
particle and composted BC (CBC; separated from mixed All data were expressed as means and standard deviations
final composting materials) particle. A solar Thermo MkII- compared statistically by Tukey’s t test at the 5% level with
6 atomic absorption spectrometer with deuterium back- SPSS11.5 (SPSS for windows, version 11.5, USA). Any
ground corrector was used to determine the contents of differences between values with p>0.05 are not considered
heavy metal in compost samples. To determine the total to be statistically significant.
concentration of heavy metals, 0.5 g of sample was
digested in a 20-mL mixture of nitric, hydrochloric, and
hydrofluoric acid (in the ratio 1:1:2; Scancara et al. 2000). 3 Results
Diethylenetriaminepentaacetic acid (DTPA)-extractable
metal contents were obtained by mechanically shaking the 3.1 Chemical changes of material during composting
compost samples at a 1:5 solid to extractant ratio (w/v) for
2 h with 0.005 M DTPA+0.1 M triethanolamine solution Temporal trends of the temperature within the composting
buffered at pH 7.3 (Page et al. 1982). materials were quite similar regardless of the level of BC
amendment (Fig. 1). The compost temperature rose to 55°C
2.3 Cu2+, Zn2+, and NH4+ adsorption by fresh BC within 5 days and remained above 55°C for around 7 days.
and composted BC Afterwards, the compost temperature gradually declined and
reached ambient temperature in 30 days. Finally, the compost
Twenty milliliters of Cu2+, Zn2+ solutions with the concen- went into maturation stage until composting was completed.
trations of 200–2,000 mg L−1, or NH4+ solutions with Total organic matter of the composting materials
concentrations of 2–10 mg L–1 were added to 0.2 g of FBC/ experienced a relatively fast decline at the early stage of
CBC in order to find out if the change of surface composting and then decreased steadily over time. There
characteristic would result in the change of retaining were no significant differences in total organic matter of the
capability of bamboo charcoal to these ions. Copper composting materials among different treatments except in
sulphate pentahydrate (CuSO4·5H2O), zinc sulphate hepta- the early stage. By the end of the experiment, about 30% of
hydrate (ZnSO4·7H2O), and ammonium chloride (NH4Cl) the initial total organic matter had mineralized (Fig. 2). In
4 Environ Sci Pollut Res (2009) 16:1–9
contrast, trends in the change of TN in composting decreased with an increasing amount of BC amendment.
materials over the composting process varied with treat- The highest TN loss (674 g) was found in composting
ment. TN concentrations in the composting material with material with no BC amendment, whereas TN loss in the
lower BC amendment (<3%) decreased during the thermo- treatment with 9% BC amendment was only 240 g, a
philic phase and then increased afterwards. When the BC difference of more than 64% (Table 2).
amendment rose to more than 5%, TN concentrations in the Boehm titration is one of the most widely used methods
composting material increased over the entire composting to quantify acidic groups in charcoal. Based on this method,
process (Fig. 3). A first-order kinetic equation was used to the amount of total acid groups of BC underwent a
calculate the potentially mineralizable C (C0): significant change during the course of composting, which
increased quickly in the first 4 weeks and became stable
Cm ¼ C0 1 ekt
after 28 days of composting. Among all acidic groups, the
where Cm (mg C/kg) is the organic C mineralized at any amount of carboxylic groups increased most. As shown in
specific time, t (days), and k is the first-order rate constant. Table 3, the amount of carboxylic groups of BC increased
Similarly, the increase of N with time could be expressed up to 0.69 mmol g−1 at the end of composting, which was
as a first-order kinetics equation. Overall, the TN loss about 2.4 times higher than that of the original value
(based on mass balance) in the composting material (0.29 mmol g−1). However, the amounts of phenolic and
lactonic groups on BC surface increased only about 50%
compared with those of the original values.
Treatment Initial material Finished material N loss (g) N loss rate (%)
Pile mass (kg) Content (g kg−1) N mass (g) Pile mass (kg) Content N mass (g)
(g kg−1)
without BC amendment had decreased 29.2% and 12.0%, than that of Zn. For example, in solutions with 2,000 mg L−1
respectively, compared with the initial value before com- of Cu2+ and Zn2+, the amounts of Cu2+ adsorbed on FBC
posting began. Furthermore, significant effects of BC was 36.0 mmol g−1, whereas Zn2+ adsorbed on FBC was
amendment on the reduction of DTPA-extractable Cu and only 14.2 mmol g−1. Results in Table 4 also indicate that the
Zn in composting material were observed during compost- retention of Cu2+ and Zn2+ by FBC and CBC decreased as
ing, with the effects differing considerably depending on initial adsorption of these two metals increased. The Cu2+
the BC amendment level. For DTPA-extractable Cu, a retention against DTPA extraction on FBC and CBC
significant difference between the BC amendments and the decreased from 88.0% to 74.0% and 88.2% to 75.0%,
non-BC control was detected when the addition of BC was respectively. Retention of Zn2+ on FBC and CBC decreased
higher than 3%. For DTPA-extractable Zn, a difference from 69.8% to 53.5% and 70.0% to 52.1%, respectively.
between the BC amendments and the non-BC control was However, according to the result of Tukey’s t test, no
found only when the BC amendment was larger than 5%. difference was observed between the retention capability of
Compared with the original value before composting, the FBC and CBC for Cu2+ and Zn2+. According to Nishantha
DTPA-extractable Cu and Zn in the treatment with 9% BC Fernando et al. (2005), the retaining of NH4+ against Ca2+
amendment decreased 44.4% and 19.3%, respectively, over exchange can express the retaining capacity of absorbent to
the course of composting. Overall, in contrast to the non- NH4+; therefore, CaCl2 was adopted as extracting solvent in
BC control, DTPA-extractable Cu and Zn contents in desorption test to determinate the retaining rate of BC to
composting materials could be further reduced by 27.5% NH4+. In this research, the retention of NH4+ against Ca2+
and 8.2%, respectively, with 9% BC amendment. exchange on FBC decreased with increasing adsorption on
BC (Table 5), a pattern of behavior similar to that of Cu2+
3.3 Cu2+, Zn2+, and NH4+ adsorption by BC before and Zn2+. However, the retention of NH4+ on CBC did not
and after composting decrease significantly with an increase of adsorption. A
significantly greater retention of NH4+ was observed by
As shown in Table 4, the amount of Cu adsorbed onto BC CBC compared to FBC, which indicated that composting has
was much higher than that of Zn, which was consistent with a significantly positive effect on the adsorption capability of
the fact that DTPA-extractable content of Cu decreased more BC for NH4+.
Sample Carboxylic groups Phenolic and lactonic groups (mmol g–1) Total acidic functional groups (mmol g–1)
(mmol g–1)
Amount values of surface functional groups followed by different small letters within the same vertical column are different significantly at 5%
level
6 Environ Sci Pollut Res (2009) 16:1–9
Table 4 Results of adsorption–desorption tests of Cu and Zn on fresh bamboo charcoal and composted bamboo charcoal (p<0.05)
Concentration Cu Zn
of solution
for adsorption FBC CBC FBC CBC
test (mg L−1)
Sorption Retention rate Sorption Retention rate Sorption Retention rate Sorption Retention rate
value (%) value (%) value (%) value (%)
(mmol g−1) (mmol g−1) (mmol g−1) (mmol g−1)
Sorption values followed by different small letters within the same vertical column are different significantly at 5% level. Retention rate followed
by different capital letter of BC and CBC transversely are different significantly at 5% level
agricultural fields. However, there have been no studies tendency for covalent bonding (higher electronegativity) of
prior to this research about the effect of biocharcoal and Cu. In addition, the results of adsorption–desorption tests
especially BC on nitrogen conservation during the course of showed that the retention of Cu2+ and Zn2+ on FBC and
composting. CBC decreased with increasing adsorbate loading. Accord-
DTPA-extractable content of heavy metals can estimate ing to the adsorption theory mentioned above, this decrease
the mobility of heavy metals in most cases (Hseu 2006; could be explained by saturation of the strong binding sites
Fang and Wong 1999). In comparison with the original on the absorbent. Moreover, there was no significant
values before composting, DTPA-extractable contents of difference in Cu2+ and Zn2+ retention by FBC compared
Cu2+ and Zn2+ in treatment with 9% BC decreased by to CBC, thus suggesting that BC oxidation during
44.4% and 19.3%, respectively, over the course of composting had no evident effect on the adsorption of
composting. In contrast to the non-BC control, DTPA- Cu2+ and Zn2+ by BC.
extractable contents of Cu2+ and Zn2+ in composting
material could be further decreased by 27.5% and 8.2%,
respectively, with the 9% BC amendment. This additional 5 Conclusions
decrease of extractable Cu2+ and Zn2+ in the composting
material mainly resulted from the adsorption of both metals Incorporation of BC into composting material could
by BC. The findings of Hiller and Brümmer (1997) that significantly lessen the total nitrogen loss during sludge
charcoal particles tended to accumulate heavy metals composting. TN loss decreased with an increasing amount
support this hypothesis. In addition, the results of this of BC amendment. In comparison to the non-BC control,
study indicated that BC played a more efficient role in the amendment of 9% BC reduced TN loss from the sludge
stabilization of Cu2+ than Zn2+. This stabilization discrep- composting material by 64.1% after composting. This
ancy might result from the different adsorption stability of reduction of TN loss mainly resulted from the high
BC to Cu2+ and Zn2+, which may correlate with the greater adsorption capacity of BC and the bio-oxidation of BC
Table 5 Results of adsorption–desorption tests of ammonium on fresh bamboo charcoal and composted bamboo charcoal (p<0.05)
Sorption values followed by different small letters within the same vertical column are different significantly at 5% level. Retention rate followed
by different capital letters of BC and CBC transversely are different significantly at 5% level
8 Environ Sci Pollut Res (2009) 16:1–9
particles during composting, which significantly increased Dai JY, Xu MQ, Chen JP, Yang XP, Ke ZS (2007) PCDD/F, PAH and
heavy metals in the sewage sludge from six wastewater treatment
the amount of surface acid groups, especially carboxylic
plants in Beijing, China. Chemosphere 66:353–361
groups. Fang M, Wong JWC (1999) Effects of lime amendment on availability
Mobility of heavy metals in the sludge composting could of heavy metals and maturation in sewage sludge composting.
also be reduced by the addition of BC. However, the Environ Pollut 106:83–89
Glaser B, Balashov E, Haumaier L, Guggenberger G, Zech W (2000)
stabilization effect of BC was different for Cu2+ and Zn2+.
Black carbon in density fractions of anthropogenic soils of the
DTPA-extractable contents of Cu2+ and Zn2+ in sludge Brazilian Amazon region. Org Geochem 31:669–678
composting material with 9% BC amendment dropped Hernández T, Masciandaro G, Moreno JI, García C (2006) Changes in
27.5% and 8.2%, respectively, at the end of composting as organic matter composition during composting of two digested
sewage sludges. Waste Manage 26:1370–1376
compared with that of the non-BC control. There was no Hiller DA, Brümmer GW (1997) Electron microprobe studies on soil
significant difference in the ability of FBC compared to samples with varying heavy metal contamination: part 2.
CBC to retain either Cu2+ or Zn2+, indicating that Contents of heavy metals and other elements in aggregations of
composting had little effect on the adsorption capacity of humic substances, litter residues, and charcoal particles. Z
Pflanzenernähr Bodenkd 160:47–55
BC for these heavy metals.
Hseu ZY (2006) Extractability and bioavailability of zinc over time in
three tropical soils incubated with biosolids. Chemosphere
63:762–771
6 Recommendations and perspectives Illera V, Walter I, Souza P, Cala V (2000) Short-term effects of
biosolid and municipal solid waste applications on heavy metals
distribution in a degraded soil under a semiarid environment. Sci
According to the results of the study, it is concluded that Total Environ 255:29–44
BC could be an effective amendment for nitrogen conser- Iyobe T, Asada T, Kawata K, Oikawa K (2004) Comparison of
vation and heavy metal stabilization in sludge composts. removal efficiencies for ammonia and amine gases between
woody charcoal and activated carbon. J Health Sci 50:148–153
However, further research into the effect of BC-amended Kithome M, Paul JW, Bomk AA (1999) Reducing nitrogen losses
sludge compost material on soil properties, bioavailability during simulated composting of poultry manure using absorbents
of heavy metals, and nutrient turnover in soil needs to be or chemical amendments. J Environ Qual 28:194–201
carried out prior to the application of BC-sludge compost in Liu YH, Ma LL, Li YQ, Zheng LT (2007) Evolution of heavy metal
speciation during the aerobic composting process of sewage
agriculture.
sludge. Chemosphere 67:1025–1032
Major J, Steiner C, Ditommaso A, Falcǎo NPS, Lenmann J (2005)
Acknowledgements This study was partially supported by China Weed composition and cover after three years of soil fertility
National Natural Science Fund (40432004), Project of Science and management in the central Brazilian Amazon: compost, fertilizer,
Technology Department of Zhejiang Province (2006C13066 and manure and charcoal applications. Weed Biol Manag 5:69–76
2007C03002), and Program for New Century Excellent Talents in Martins O (1992) Loss of nitrogenous compounds during composting
University. of animal wastes. Bioresour Technol 4:10–16
Nishantha Fernando WAR, Kang X, Charles WR (2005) Sorption and
desorption of ammonium from liquid swine waste in soils. Soil
Sci Soc Am J 69:1057–1065
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Amir S, Hafidi M, Merlina G, Revel JC (2005) Sequential extraction untreated/treated urban effluent and sludge from a biological
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BIOCHAR VOLATILE MATTER CONTENT EFFECTS ON PLANT
GROWTH AND NITROGEN TRANSFORMATIONS IN A TROPICAL
SOIL
ABSTRACT
Biochars made from modern pyrolysis methods have attracted widespread attention as
potential soil amendments with agronomic value. A series of greenhouse experiments
and laboratory incubations were conducted to assess the effects of biochar volatile
matter (VM) content on plant growth, nitrogen (N) transformations, and microbial
activities in an acid tropical soil. High VM biochar inhibited plant growth and reduced
N uptake with and without the addition of fertilizers. Low VM charcoal supplemented
with fertilizers improved plant growth compared with the fertilizer alone. The
laboratory experiments showed that high VM biochar increased soil respiration and
immobilized considerable quantities of inorganic N. This research shows that biochar
with high VM content may not be a suitable soil amendment in the short-term.
INTRODUCTION
The use of biochar as a soil amendment is modeled on the C-rich anthropogenic soils known
as “Terra Preta do Indio” (Indian black earth) found in Amazonia and associated with habitation
sites of pre-contact Amerindian populations dating as far back as 7,000 cal yr BP (Glaser, 2007).
The defining characteristic of Terra Preta soils is the presence of large quantities of charcoal in
the soil organic matter to depths of 1 m or greater (Glaser et al., 2000; Sombroek et al., 1993).
These soils are remarkable because they have remained fertile and enriched in soil C compared
with adjacent forest soils despite centuries of cultivation.
Recent efforts to replicate the “Terra Preta” phenomenon using biochars created from
modern pyrolysis techniques show that charcoal additions can have an ameliorating effect on
highly weathered, infertile tropical soils by increasing CEC and plant nutrient supply, reducing
soil acidity and aluminum toxicity, and improving fertilizer efficiency due to reduced nutrient
leaching (Glaser at al., 2002; Lehmann et al., 2003). Plant growth response to charcoal amended
soils has been variable with both negative and positive results reported in the scientific literature
(Glaser at al., 2002). Several studies have reported that plant growth responses are largest when
charcoal and fertilizers are combined suggesting a synergistic relationship (Chan et al., 2007;
Lehmann et al., 2003; Steiner et al., 2007). Gundale and Deluca (2007) observed that laboratory
produced charcoal from ponderosa pine and Douglas-fir had a negative effect on plant growth
whereas the same charcoal created from wildfires showed a positive effect on plant growth. The
authors speculated that the low temperature charring method used to create the charcoal in the
laboratory either created toxic compounds that inhibited plant growth or acted as a source of
labile carbon (C) stimulating microbial growth and N immobilization. The objectives of the
present research were to determine the effects of charcoal volatile matter content on plant growth
and N transformations in a tropical acid soil. We hypothesized that biochar created at low
temperatures with high VM would increase microbial activity resulting in a decrease in plant
available N due to immobilization.
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 26
MATERIALS AND METHODS
Two greenhouse bioassays and two laboratory incubations were conducted to test the effects
of biochar VM content on plant growth and N transformations. The soil was an infertile, acid
Leilehua series (very-fine, ferruginous, isothermic, ustic kanhaplohumults) collected from the
30-80 cm depth at the Waiawa Correctional Facility, Mililani, Oahu Island (N21°26’53”, W157°
57’ 52”). The charcoal feedstock used in our experiments was macadamia nut shells. The
charcoal was made using a flash carbonization process developed at the Natural Energy Institute
at the University of Hawaii (Antal et al., 2003). Selected chemical properties of the soil and
biochars used in the different experiments are presented in Table 1. Total C and N content of the
biochars were determined by dry combustion on a LECO CN-2000. Biochar pH was measure in
1:1 slurry of charcoal to deionized water. Base cations were extracted with 1M ammonium
acetate at pH 7 and Al+++ was extracted with 1M KCl and measured in solution by inductive
coupled plasma spectrophotometer. The effective cation exchange capacity (ECEC) of the
biochars and soil was determined by summing the exchangeable cations.
Table 1. Selected chemical properties of the Leilehua soil, and the biochars used in the
greenhouse and laboratory experiments (LVM = low VM content and HVM = high VM
content).
VM Ash OC TN pH P K Ca Mg Na Al ECEC
% mg kg-1 cmolc kg -1
Soil
Leilehua 4.28 0.12 4.70 2.22 0.09 0.72 0.52 0.29 1.61 3.22
Charcoal
LVM
6.30 4.18 88.7 0.45 8.16 17.2 1.25 3.7 0.31 0.011 22.5
MacNut
HVM
22.5 3.33 85.2 0.45 5.72 18.5 0.74 0.7 0.15 0.032 20.2
MacNut
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 27
study, the biochar was mixed thoroughly with 50 g (oven dry equivalent) of soil followed by the
addition of the appropriate volume of deionized water required to bring the soil to 75% of water
holding capacity. The soils were placed in 100 mL beakers, weighed at the outset of the
incubation, covered with perforated parafilm, and incubated at constant temperature (28°C) and
moisture. Soils were sampled and analyzed for inorganic N, protease activity, and K2SO4
extractable organic C and TN after 2, 7, and 14 days. The soluble C fraction of the biochar was
determined by shaking 3 g of biochar in 30 mL deionized water for 1 hour and filtering through a
45 μm nylon membrane. For the CO2 respiration study, we used the alkali adsorption method
where 50 g of treated and untreated soils and 50 ml of 0.05 M NaOH were sealed in airtight 1 L
mason jars and incubated at 28°C for 14 days (Alef, 1995). The beaker containing the NaOH
solution was removed from the mason jar at 48 hour intervals and titrated with 0.05 M HCl
following the addition of 0.5 M BaCl2. Four mason jars with the 0.05 M NaOH solution, but
without soil were used as controls.
4
combined with charcoal. Indeed, by
Shoot Biomass ( g pot-1)
fertilizers significantly increased tissue N, P, Figure 1. Treatment effects on above ground corn dry
and K concentrations and the accompanying matter production in an infertile Leilehua soil amended
significant rise in dry matter production with high VM biochar and fertilizer (S = soil, S+C =
indicated that the Leilehua soil was severely soil + biochar, S+L = soil + lime, S+F+L = soil + NPK
deficient in N, P, and K. The biochar in + lime, S+C+F = soil + biochar + NPK).
combination with fertilizers, however,
significantly decreased tissue N, P, and K concentrations compared to the fertilizer control
treatment. Our observations were in disagreement with a recent greenhouse experiment reporting
that biochar significantly improved N fertilizer use efficiency by radish plants (Chan et al.,
2007). We speculated that the relatively high VM content of the biochar used in this experiment
may have played a role in inhibiting corn growth.
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 28
The results of the second greenhouse experiment showed that biochar VM content had
significant effects on plant growth. High VM biochar significantly reduced shoot dry matter
compared with the control whereas low VM biochar had no significant effect on dry matter
production (Fig. 2). Corn growth was
significantly better in the low VM 0.4
b
charcoal treatment than in the high VM a
30
and the researchers speculated that the
decline in plant growth was caused by 20
Soil
Soil+HVM
N immobilization due to high Soil+LVM
Days
experiments confirmed that biochar
VM exerts a strong influence on N +
mineralization and microbial Figure 3. Biochar effects on soil NH4 -N in a 14 - day
incubation.
respiration. The untreated soil showed
an initial drop in soil NH4+-N after two
days from 39.4 to 31.7 mg kg-1 followed by a slow increase to 45.3 and 43.4 mg kg-1 after seven
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 29
and fourteen days respectively (Fig. 3). The soil amended with high VM biochar, however,
showed a dramatic decline in soil NH4+-N that persisted throughout the fourteen day incubation.
The low VM biochar had a much smaller effect on soil NH4+-N decreasing it to around 30 mg
kg-1. In the CO2 respiration study, the high VM biochar amendment caused a steep increase in
respiration reaching a peak at four days followed by a gradual decline through the 12th day (Fig.
4). At day 2 and day 6 the high VM
biochar treatment showed a respiration 400
-1
300
the control throughout the remainder of
-1
the incubation period. The low VM
treatment showed an initial spike in 200
respiration at day 2 followed by a rapid
decline matching the control values by
the eighth day. The relatively high CO2 100
Days
N immobilization by the microbial
biomass was an important factor Figure 4. Biochar effects on CO2 respiration in a 12-day
explaining the observed decline in plant incubation.
growth and N uptake in the high VM
biochar treatments. The high water extractable C content of the high VM biochar (265 mg C kg-
1
) compared with the low VM biochar (53 mg kg-1) provided a labile source of C fueling the
observed stimulation of microbial activity in the high VM treatment. With the high C:N ratio of
the biochar, the microbial biomass was forced to scavenge soil N inducing N deficiency in the
growing plants.
SUMMARY
This research shows that biochar VM content, or the degree of carbonization, can play a
critical role in determining its agronomic value as a soil amendment. Our results provide clear
evidence that biochars that are high in VM content (i.e., a typical barbecue charcoal) would not
be good soil amendments because they can stimulate microbial activity and immobilize plant
available N in the short-term. On the other hand, more fully carbonized biochars with lower VM
content containing a smaller labile C component have a smaller effect on soil microbial activity
and N immobilization. While our research provides one explanation for why some biochars have
a negative effect on plant growth, it still remains unclear why low VM biochars in combination
with fertilizer appear to have a beneficial effect on plant growth. Despite our findings elucidating
the role of VM content in inhibiting N mineralization, research at the field scale is required to
truly assess the agronomic value of biochars as soil amendments.
REFERENCES
Alef, K. 1995. Soil Respiration, p. 214-216, In K. Alef and P. Nannipieri, eds. Methods in
applied soil microbiology and biochemistry. Academic Press, London.
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 30
Antal, M.J., K. Mochidzuki, and L.S. Paredes. 2003. Flash carbonization of biomass. Industrial
& Engineering Chemistry Research 42:3690-3699.
Chan, K.Y., L. Van Zwieten, I. Meszaros, A. Downie, and S. Joseph. 2007. Agronomic values of
greenwaste biochar as a soil amendment. Australian Journal of Soil Research 45:629-634.
Glaser, B. 2007. Prehistorically modified soils of central Amazonia: a model for sustainable
agriculture in the twenty-first century. Philosophical Transactions of the Royal Society B-
Biological Sciences 362:187-196.
Glaser, B., E. Balashov, L. Haumaier, G. Guggenberger, and W. Zech. 2000. Black carbon in
density fractions of anthropogenic soils of the Brazilian Amazon region. Organic
Geochemistry 31:669-678.
Glaser, B., J. Lehmann, and W. Zech. 2002. Ameliorating physical and chemical properties of
highly weathered soils in the tropics with charcoal - a review. Biology and Fertility of Soils
35:219-230.
Gundale, M.J., and T.H. DeLuca. 2007. Charcoal effects on soil solution chemistry and growth
of Koeleria macrantha in the ponderosa pine/Douglas-fir ecosystem. Biology and Fertility of
Soils 43:303-311.
Hue, N.V., R. Uchida, and M.C. Ho. 2000. Sampling and analysis of soils and plant tissues. pp.
23-30, In J. A. S. a. R. S. Uchida, ed. Plant Nutrient Management in Hawaii Soils. College
of Tropical Agriculture and Human Resources, University of Hawaii, Honolulu.
Lehmann, J., J.P. da Silva, C. Steiner, T. Nehls, W. Zech, and B. Glaser. 2003. Nutrient
availability and leaching in an archaeological Anthrosol and a Ferralsol of the Central
Amazon basin: fertilizer, manure and charcoal amendments. Plant and Soil 249:343-357.
Sombroek, W.G., F.O. Nachtergaele, and A. Hebel. 1993. Amounts, dynamics and sequestering
of carbon in tropical and subtropical soils. Ambio 22:417-426.
Steiner, C., W. Teixeira, J. Lehmann, T. Nehls, J. de Macêdo, W. Blum, and W. Zech. 2007.
Long term effects of manure, charcoal and mineral fertilization on crop production and
fertility on a highly weathered Central Amazonian upland soil. Plant and Soil 291:275-290.
ACKNOWLEDGEMENTS
We thank Dr. Michael Antal for providing biochar samples along with proximate analysis
data and Yudai Tsumiyoshi and Jocelyn Liu for assistance with laboratory analysis. Funding for
this research came in part from USDA HATCH project 863H.
Western Nutrient Management Conference. 2009. Vol. 8. Salt Lake City, UT. Page 31
Copyeditor: Maria Timothy Santiago
TECHNICAL ARTICLE
thick) that have sand, loamy sand, or sandy loam textures; and
Abstract: Agricultural soils in the southeastern U.S. Coastal Plain relatively thick Bt horizons (1.0Y3.0 m thick) with sandy clay to
region have meager soil fertility characteristics because of their sandy clay textures (Daniels et al., 1970; Shaw et al., 2004). Intensive
textures, acidic pH values, kaolinitic clays, low cation exchange capaci- leaching of bases has resulted in low soil pH values, extensive
ties, and diminutive soil organic carbon contents. We hypothesized that clay mineral weathering, low cation exchange capacity (CEC)
biochar additions will help ameliorate some of these fertility problems. values (2Y8 cmolc kgj1), and high levels of exchangeable Al
The study objectives were to determine the impact of pecan shellYbased (Gamble and Daniels, 1974; Daniels et al., 1978). These soil
biochar additions on soil fertility characteristics and water leachate characteristics severely limit soil fertility and agricultural man-
chemistry for a Norfolk loamy sand (fine-loamy, kaolinitic, thermic typic agement options.
Kandiudults). Soil columns containing 0, 0.5, 1.0, and 2.0% (wt/wt) For instance, sandy soils exhibit high N leaching after fer-
biochar were incubated at 10% (wt/wt) moisture for 67 days. On days tilizer or manure application (Trindale et al., 1997; Ritter et al.,
25 and 67, the columns were leached with 1.2 to 1.4 pore volumes of 1998; Zotarelli et al., 2007). Moreover, Ultisols in the Coastal
deionized H2O, and the leachate chemical composition determined. On Plain region have low soil organic carbon (SOC) contents in the
days 0 and 67, soil samples were collected and analyzed for fertility. The surface 0- to 15-cm depth (6.3Y9.2 g kgj1; Hunt et al., 1996;
biochar had a pH of 7.6, contained 834.2 and 3.41 g kgj1 of C and N, Novak et al., 2007a) because of rapid residue oxidation, which is
respectively, and was dominated by aromatic C (58%). After 67 days and further accelerated by inversion tillage for row crop production
two leaching events, biochar additions to the Norfolk soil increased soil (Bauer et al., 2006). The physical and chemical problems dis-
pH, soil organic carbon, Ca, K, Mn, and P and decreased exchangeable cussed above severely limit soil fertility and hence crop pro-
acidity, S, and Zn. Biochar additions did not significantly increase soil ductivity on the Ultisols of the southeastern U.S. Coastal Plain.
cation exchange capacity. Leachates contained increasing electrical con- Fertility problems associated with southeastern Coastal
ductivity and K and Na concentrations, but decreasing levels of Ca, Plain Ultisols are similar to those of Oxisols in intertropical
P, Mn, and Zn. These effects reflect the addition of elements and the regions (Eswaran and Tavernier, 1980), which also have low pH,
higher sorption capacity of biochar for selective nutrients (especially Ca, SOC, and CEC values (Tiessen et al., 1994; Lehmann et al.,
P, Zn, and Mn). Biochar additions to the Norfolk soil caused significant 2003). Poor soil fertility raises concerns about the sustainability
fertility improvements. of agriculture in regions dominated by Oxisols and has spurred
Key words: Biochar, coastal plain soil, fertility, GRACEnet, leachate the development of management practices to restore or im-
prove their fertility status (Glaser et al., 2002). Applications of
(Soil Sci 2009;174: 00Y00)
mulches, composts, and manures increase soil fertility; however,
under tropical conditions, the increase is short term because the
added organic matter is quickly oxidized and added bases are
To predict the reactivity as well as stability of biochar when elemental concentrations (Ca, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, P,
used as a soil amendment, it is important to know the biochars Si, and Zn expressed on a dry, wt/wt, ash-free basis) in the
organic structural composition. Biochar from Terra Preta soils biochar digests were measured using an Elan DRC-II (Perkin-
analyzed using solid-state nuclear magnetic resonance (NMR) Elmer, Shelton, CT) inductively coupled plasma mass spec-
analysis was shown to be composed of a highly heterogeneous trometer. Analytical operating conditions and element detection
mixture of organic structures (Novotny et al., 2007). The struc- limits are available at EBG-SWES-UA (2008).
tural form of C in biochar depends on the biogeochemistry of the Solid-state cross-polarization magic angle-spinning total-
biomass feedstock and the conditions under which it was py- sideband suppression 13C NMR spectral pattern of the biochar
rolyzed (Kramer et al., 2004; Lehmann, 2007). Biochars com- was obtained using a Bruker DSX-300 spectrometer (Karlsruhe,
posed primarily of condensed aromatic C are known to persist in Germany) operated at a 13C frequency of 75.5 MHz. Additional
soil environments for millennia, whereas biochars with higher technical parameters to acquire the spectra have been described
levels of single-ring aromatic and aliphatic C will mineralize by Wang et al. (2007). The chemical shift region assignments
more rapidly (Lehmann, 2007; Novotny et al., 2007). Surface were as follows: 0 to 50 ppm, aliphatic C; 50 to 109 ppm,
area and surface charge density of biochar will have a large O-alkyl C; 109 to 163 ppm, aromatic C; and 163 to 190 ppm,
influence on soil CEC and the ability of biochar additions to carboxylic C. The percent C distribution was determined by
ameliorate soil fertility problems. estimating the area in these chemical shift regions as a per-
We hypothesize that biochar additions to the sandy, Coastal centage of the total area under the spectral curve.
Plain soils of the southeastern United States would increase
the SOC content and CEC and improve the fertility status. The Norfolk Soil Collection and Analyses
specific objectives of this investigation were to determine the 1) A bulk sample of a Norfolk soil from the Ap horizon
chemistry of biochar derived from pyrolysis of pecan shells, a (0Y15 cm deep) was collected from a field contiguous to the
locally abundant source of feedstock; 2) effects of biochar addi- USDA-ARSYCoastal Plain Research Center, Florence, SC. The
tions on fertility characteristics of a Norfolk soil; and 3) effects field is nearly level (1Y2% slopes) and has a 30-year history of
of biochar additions on the chemical composition of leachate row crop production (Sojka et al., 1984). The soil was collected
collected from a Norfolk soil. using a shovel in mid-April, approximately 1 week after fertili-
zation with 49 kg N haj1 of 28-0-0 UAN (urea + NH4NO3) for
MATERIALS AND METHODS an upcoming corn crop. The soil was air dried and 2-mm sieved.
The Ap horizon is a loamy sand with a particle size distribution
Production and Characterization of Pecan of 730, 250, and 20 g kgj1, respectively, of sand, silt, and clay
ShellYBased Biochar (sedimentation method; Soil Characterization Lab, Ohio State
Pecan shells were obtained from a supplier in Lumberton, University, Columbus, OH). X-ray diffraction analysis of the
NC. They were ground using a Retsch Mixer Mill (SR-2000; clay fraction revealed a preponderance of kaolinite, with minor
Cole-Palmer, Vernon Hills, IL) to pass through a 2-mm sieve. amounts of hydroxy (Fe and Al) interlayered chlorite (X-ray
Per each pyrolysis batch, approximately 1000 to 2000 g of shells diffraction method; Soil Characterization Lab, Ohio State Uni-
were placed into a crucible (25 cm wide ! 10 cm deep) and were versity). The pH of the untreated Norfolk Ap soil was 4.8, as
inserted into a Lindberg box programmable furnace equipped measured in a 1:1 soil-to-deionized water mixture (Novak et al.,
with an airtight retort (model 5116HR; Lindberg, Watertown, 2007a). The total C and total combustible nitrogen (TCN)
WI). The furnace retort atmosphere was purged with N2 using contents were determined using a LECO TruSpec CN analyzer
a flow rate of 0.1 m3 hj1. The furnace was controlled with a (LECO Corp., St Joseph, MI). Soil C was assumed to be organic
multiple-step pyrolysis temperature program. The furnace was in nature because the low soil pH precluded carbonates.
initially heated to 40 -C; temperature was ramped to 170 -C at
5 -C minj1 and was maintained at this temperature for 30 min. Biochar Incubation in Norfolk Ap Soil
The temperature was then ramped to 700- C at 5 -C minj1, The biochar incubation experiment was conducted in open-
and the pecan shells were subjected to pyrolysis for 1 h. The top, 10-cm-diameter, 17-cm-tall schedule-40 PVC columns.
biochar was cooled in the oven under the N2 atmosphere over- Column bottoms were sealed using a nylon mesh fabric to
night. After cooling, the biochar was ground to pass through a support the soil bed and minimize soil loss. Sufficient amounts
0.25-mm sieve. of 0.25-mm sieved biochar was mixed into 750-g of air-dried,
The sieved biochar moisture percent (wt/wt) content was 2-mm-sieved Ap horizon soil to create 0, 0.5, 1.0, and 2.0%
measured by oven drying a 2-g portion overnight at 80 -C. (wt/wt) biochar treatments. These biochar rates equated to field
Biochar pH was measured according to Ahmedna et al. (1998). applications of approximately 0, 10, 20, and 40 metric tons haj1.
The method consisted of preparing a 1% (wt/wt) suspension of Each treatment was set up in triplicate. Deionized H2O was
biochar in deionized water. The suspension was heated to about then mixed into each treatment to obtain a soil-moisture content
90 -C and stirred for 20 min to allow dissolution of the soluble of 10% (wt/wt), representing the upper range (between 5 and
biochar components. After cooling to room temperature, the pH 10%) of field capacity for a typical Norfolk Ap soil horizon. The
of the biochar suspension was measured using a Corning pH moist soil treatments were then placed into columns, and they
meter (Acton, MA). The biochar percent ash content (wt/wt) was were tamped down by hand to obtain a bulk density of 1.2 g cm3.
determined by dry combustion at 760 -C in air for 6 h using an This created a headspace above the soil of 8 to 10 cm for adding
AQ1 Isotemp laboratory muffle furnace (Fisher Scientific). Biochar water. The columns were laboratory incubated for 67 days at 10%
percent moisture was 1.4%, pH was 7.5, and ash content was soil moisture. The laboratory room temperature and percent
3.8% (wt/wt). relative humidity, respectively, throughout the incubation ranged
A sample of the biochar was analyzed for total C, H, N, S, between 17 and 27 -C and 23 and 61%.
and O (by difference) determination using ASTM D 3176 On days 25 and 67, each column was leached with 1.2 to 1.4
method (ASTM, 2006). For total elemental analyses, the biochar pore volumes of deionized water; the leachate was collected and
was redried and then digested using the EPA method 3052 weighed. The leachates were analyzed for total organic carbon
microwave-assisted acid digestion method (USEPA, 2008). The (TOC) concentrations using a Shimadzu TOC-Vcs (Shimadzu
Copyright @ 2009 by Lippincott Williams & Wilkins. Unauthorized reproduction of this article is prohibited.
Soil Science & Volume 174, Number 2, February 2009 Biochar in Coastal Plain Soil
FIGURE 1. 13C NMR spectral pattern for pecan shellYbased biochar (%C distribution for structural groups determined as described by
Wang et al. (2007).
Corp., Columbia, MD), and for Ca, Cu, Fe, K, Mg, Mn, Na, P, S, structures of the biochar. This speculation has merit because
and Zn concentrations with a Varian ICP-OES (Varian Inc., Palo the high pyrolysis temperature explains the lack of alkyl C
Alto, CA). The ICP detection limit for this suite of 11 elements (0Y50 ppm) as volatile material such as oils, fatty acids, and
was a conservative 0.05 mg Lj1. The leachate pH and electrical alkyl alcohols would be lost (Antal and GrLnli, 2003). Carboxyl-
conductivity (EC) were measured using a standard pH and a containing structures were present in the NMR spectra possibly
conductivity meter. because of their structural decomposition resistance during
Samples of the biochar-treated Norfolk Ap soil were col- pyrolysis. Alternatively, their presence could be due to water
lected on incubation days 0 and 67 for analysis of plant available sorption during handling and grinding. The biochar percent
nutrients using Mehlich 1 (diluted HCl and H2SO4) extractant. moisture after grinding and before total elemental analyses was
Measurements of Mehlich 1Yextractable Ca, Cu, Fe, K, Mg, less than 2% and 4%, respectively. Consequently, single-ring
Mn, Na, P, S, and Zn and exchangeable acidity values were aromatic and some heterocyclic compounds could have been
conducted by the Clemson University Soil Testing Laboratory reoxidized, forming carboxylic and acetyl OH groups as evident
using ICP. The pH and EC of the biochar-treated Norfolk Ap
soil were measured using the methods of Novak et al. (2007a).
Statistics TABLE 1. Total elemental analyses of pecan shellYbased
The mean values of SOC and TCN contents between the biochar and Norfolk Ap soil† (data sorted into macroelement,
treatments, sorted by incubation day, were tested using a one- microelement pools)
way analysis of variance (ANOVA) with a P G 0.05 level of
Biochar Norfolk Ap soil
significance. The soil fertility characteristics and chemical com-
position of the deionized water leachates were sorted and tested Macroelement (g kgj1)
in a similar manner. All statistical tests were performed using Al 0.22 5.1
SigmaStat v. 3.5 software (SSPS Corp., Chicago, IL). C 834.2 16.8
Ca 3.64 0.49
RESULTS AND DISCUSSION Fe 0.07 2.91
Biochar and Soil Compositional Analyses H 10.3 V
F1 The 13C NMR spectral pattern of the pecan biochar (Fig. 1) K 4.15 0.38
revealed two prominent peaks at 120 and 187 ppm and a N 3.41 1.26
shoulder near 90 ppm. These peaks indicate that most of this O 19.8 V
biochar is distributed in aromatic structures (58%), with less Si 104.9 424.8
amounts of C having single bonds to O (29%) and in carboxyl Microelements (mg kgj1)
(13%) groups. The lack of a distinct peak near 75 ppm suggests Cu 14 4.6
little carbohydrate C; rather, the shoulder near 90 ppm is more Cr 0.31 23
characteristic of acetal C (Wershaw, 1985). The pecan shells Mg 698 445
used as feedstock for preparation of the biochar are composed
Mn 78 55
primarily of lignin and cellulose (47%, acid-detergent lignin;
Na 218 951
Ramirez et al., 1986). Charring of lignin and cellulose at tem-
peratures of 500 -C was reported to cause loss of their aliphatic Ni 0.5 2
components along with a conversion of ring structures into P 263 185
aromatic compounds (Rutherford et al., 2004). During pyrolysis S 95 2
at 700 -C in this study, it was suspected that a similar decom- Zn 7 43
position of cellulose and lignin and structural rearrangement of †
Determined on biochar and soil using EPA 3052 method (HNO3 + HF).
ring compounds to form condensed and single-ring aromatic
TABLE 3. Fertility characteristics of Norfolk Ap soil + percent biochar mixtures on 0- and 67-day incubations
(Mehlich 1 extractant)†
Fertility characteristics‡
§
Incubation pH CEC Exch. acid Ca Cu K Mg Mn Na P S Zn
Norfolk Ap
j1 j1
soil + % biochar day - - - - - -cmolc kg ------- - - - - - - - - - - - - - - - - - - - - - - mg kg ----------------------
a a a a a a a a
0 0 4.8 5.7 2.4 437 0.6 35 117 12 5a 30.5a 8.67a 13a
0.5 0 5.1b 5.3a 2.0a 470b 0.7a 49b 98b 7b 5a 30.8a 7.67a 12a
1.0 0 5.5c 5.4a 1.9a 516c 0.7a 66c 90c 15c 6a 31.2a 7.83a 11a
2.0 0 6.3d 5.9a 1.2b 720d 0.8a 111d 91d 10d 7b 35.2b 8.50a 11a
0 67 5.2a 5.2a 2.4a 392a 0.6a 26a 93a 7a 3a 28.7a 6.33a 12a
0.5 67 5.6b 5.4a 2.1a 462b 0.7a 47b 91a 6a 5b 31.7b 5.16a 11b
1.0 67 5.9c 5.6a 2.0a 537c 0.7a 49c 92a 16b 4a 31.7c 4.00b 11b
2.0 67 6.4d 5.9a 1.5b 692d 0.8a 69d 89a 10c 4a 33.3d 3.17c 10c
†
Extracted with H2SO4 + HCl.
‡
Mean values sorted by incubation day were compared using a one-way ANOVA for multiple-comparisons tests vs. a control (Norfolk Ap soil +
0% biochar).
§
Means followed by a different letter are significantly different at P G 0.05.
Copyright @ 2009 by Lippincott Williams & Wilkins. Unauthorized reproduction of this article is prohibited.
Soil Science & Volume 174, Number 2, February 2009 Biochar in Coastal Plain Soil
the biogenic humic material and much older dates for the black 1995). Aqueous monomeric hexahydronium [Al(H2O)6]+3 spe-
C fraction. Therefore, soil applied biochar has the potential to cies act as pH buffers because they can undergo rapid and
increase the recalcitrant pool of soil C and will persist in soil reversible hydrolysis reactions influencing solution pH values
environments much longer than C added in the form of residues by liberating or accepting H+1 (Sparks, 1995). For soil pH to
or biogenic soil organic matter. change, the biochar itself or a cation in the biochar must react
Biochar additions to soils are reported to improve soil fer- with the soluble monomeric Al species or displace it from ex-
tility by raising soil CEC (Liang et al., 2006). Soil CEC increases change surfaces on clays or soil organic matter. At pH 4.8, the
are due to carboxylate groups on the surfaces of the biochar itself Norfolk soil with no biochar had 42% (2.4 cmolc exchangeable
and to exposed carboxylate groups of organic acids sorbed by the acidity kgj1 " 5.7 cmolc CEC kgj1 ! 100; Table 3) of the total
biochar, both of which contribute negative surface charge to soil CEC sites occupied by [Al(H2O)5]+2. This would be the
biochar particles (Liang et al., 2006). Biochar in this experiment dominant monomeric Al species in the Norfolk Ap soil + 0%
contained some carboxyl characteristics (13%; Fig. 1); yet, the biochar at pH 4.8 (Sparks, 1995). Additions of 0.5 and 1%
ability of biochar additions to increase the soil CEC even at 2% biochar to the Norfolk soil did not significantly modify the ex-
T3 biochar addition was negligible (Table 3). One might expect after changeable acidity values, although soil pH values significantly
a 67-day incubation that additional carboxylate groups would increased by 0.7 U (Table 3). With the addition of 2% biochar,
form because of oxidation of the biochar surfaces (Schmidt and the pH increased from 4.8 to 6.3, and exchangeable acidity was
Noack, 2000). However, differences in Norfolk Ap CEC values reduced by 50% ($1.2 cmolc kgj1; Table 3). Thus, biochar was
for the day-0 and day-67 samples were negligible (Table 3). an effective liming agent, neutralizing solution pH and reducing
The high pyrolysis temperature (700 -C) may have con- exchangeable acidity values. However, substantial additions of
tributed to the relatively low level of surface oxidation of the biochar (2% or 40 metric tons haj1) were required to obtain in-
pecan shell biochar and hence the lack of a significant impact of creases in pH and reductions in exchangeable acidity.
biochar additions on the CEC of the Norfolk Ap horizon soil. During pyrolysis, cations (primarily K, Ca, Si, and Mg) pre-
Higher pyrolysis temperatures generally cause greater conden- sent in the pecan shells formed metal oxides (e.g., ash) that were
sation of aromatic structures and even the formation of graphitic admixed with the biochar. Once in the soil environment, these
cores (Antal and GrLnli, 2003). Such highly condensed aromatic oxides can react with H+1 and monomeric Al species, modifying
C has less surface area and fewer oxidizable surface functional soil pH and exchangeable acidity values. Because the biochar
groups than more open (less condensed) aromatic C structures. contained a high Ca concentration (3.64 mg kgj1; Table 1),
High-temperature biochars are also more resistant to chemical Reaction (1) involving CaO exemplifies the liming ability of the
oxidation and microbial degradation and hence have a longer ash associated with the biochar:
half-life in soil environments than soil organic matter. The re-
calcitrant characteristics of high-temperature biochar, however, 2Al # soil þ 3CaO þ 3H2O Y 3Ca # soil þ 2A1ðOHÞ3 ð1Þ
would be a desirable property if the primary goal was to remove During this reaction, Ca replaces the monomeric Al species
atmospheric CO2 and sequester C in soil for millennia (Laird, on soil mineral or soil organic matter CEC sites. Accompanying
2008). On the other hand, if the primary goal was to increase soil this reaction is an increase in soil solution pH caused by the
CEC values, then the addition of biochar prepared by pyrolysis depletion of the readily hydrolysable monomeric Al and the for-
of feedstocks at lower temperatures (400Y500 -C) or under mation of the more neutral [Al(OH)3]0 species (Sparks, 1995).
different moisture and pressures conditions (Antal and GrLnli, This general reaction explains the decline in exchangeable
2003) may be more desirable. Low-temperature biochars will acidity for the Norfolk Ap soil and the increase in solution pH
most likely also increase soil C sequestration, but they will prob- and Ca on CEC sites (Table 3). The pH increase and exchange-
ably more rapidly change soil fertility characteristics when com- able acidity decrease were similar for the day-0 and day-67
pared with using high-temperature biochars. samples. This suggests that the liming effect of biochar occurred
Some microbial oxidizable compounds such as anhydrocel- rapidly and was sustainable on equilibration.
lulose (dehydrated forms of cellulose), polysaccharides, alcohols, The biochar significantly increased some important plant
and so on, should exist in biochars prepared by pyrolysis of macronutrients. Mehlich 1Yextractable Ca, K, and P all increased
feedstocks at lower temperatures (Antal and GrLnli, 2003). with the level of biochar additions (Table 3). However, the P
Baldock and Smernik (2002) and Hamer et al. (2004) both increase was significant only at the highest level of biochar ad-
reported a relationship between biochar pyrolysis temperature dition. By contrast, Mehlich 1Yextractable Mg decreased with
and resistance to soil microbial decomposition. Hamer et al. increasing biochar addition at day 0, suggesting that the Mg was
(2004) found that biochars produced from maize and rye at strongly retained by the biochar. Extractable S and Zn concen-
350 -C were more prone to soil microbial degradation than trations also decreased slightly with increasing biochar additions,
biochar made from oak wood pyrolyzed at 800 -C. The authors but the trend was significant only for the day-67 samples. Copper
attributed differences in biochar decomposition because of their concentrations were not significantly affected by biochar addi-
C:N ratios; higher pyrolysis temperatures caused wider C:N tions, and Mn concentrations were variable. The observed varia-
ratios in the oak wood biochar because of loss of N and con- tions in Mehlich 1Yextractable plant nutrient concentrations, at
centration of C (Hamer et al., 2004). days 0 and 67, reflected the combined effects of fertilization
Upon decomposition and oxidation by soil microbial com- (nutrients added with the biochar), leaching of nutrients, and
munities, these organic carbon structures should produce by- nutrient adsorption by the soil and added biochar. No plants were
products containing a higher density of carboxylate and other grown in these soils, and hence, plant uptake was not a variable in
O-containing functional groups (i.e., jOH, jOR, etc.) capable of this study. In general, biochar additions increased the levels of
serving as sites for cation exchange (Stevenson, 1994). Therefore, plant macronutrients and had little effect on micronutrients.
when creating biochars for use as a soil fertility amendment, the
biomass pyrolysis conditions could be designed to carbonize the Chemical Composition of the Water Leachates
material under moist conditions and at lower temperatures. It is important to examine the chemical composition of a
Research has shown that soil pH is more influenced by deionized water extract of an amended soil; in some cases, the
monomeric Al species on exchange sites than by H+1 (Sparks, amendment can release elements that may cause plant growth
TABLE 4. Chemical composition of deionized water leachates from Norfolk Ap soil + percent biochar mixtures after 25- and
67-day incubation†
‡
Mean values sorted by incubation day were compared using a one-way ANOVA for multiple comparisons vs. a control (Norfolk Ap soil +
0% biochar, significant digits varied because of low mean element concentrations on day 67).
§
Means followed by a different letter are significantly different at P G 0.05.
issues (Novak et al., 2007b). For the 25- and 67-day leachates, pH, combination of reactions such as retention of o-PO4j3 through
EC values, and TOC concentrations (except 0.5% on day 25) were ligand exchange reactions involving O-containing functional
T4 similar for the biochar-treated soils and control soils (Table 4). groups on the biochar surface, adsorption of o-PO4j3 by Fe and
The cation concentrations in the 25- and 67-day leachates Al oxides and hydroxides, and by adsorption and precipitation by
seem to be influenced by cation valency. For instance, the Ca, Mg-phosphates (Bohn et al., 1979). Regardless of sorption
monovalent cation (K and Na) concentrations in both the 25- and mechanisms, these results suggest that biochar has the potential
67-day leachates increase with the level of biochar addition to to ameliorate P leaching in soils with sandy textures, a common
the Norfolk Ap soil, whereas concentrations of multivalent problem in fields containing excess soil P concentrations as a
cations (Ca, Mg, Mn, and Zn) all decreased for the day-27 result of overapplication of swine manure (Novak et al., 2000).
leachates and either decreased or were not significantly different
for the day-67 leachates with increasing levels of biochar ad- Net Norfolk Ap Soil Fertility Changes
dition. The strength of cation retention or repulsion from nega- The net soil fertility change to the biochar-treated Norfolk
tively charged surfaces increases with increasing ion charge and Ap soil is presented in Table 5. The results after adding 2% T5
with distance between the charged surface and either the source biochar were presented because this treatment caused the most
of charge or the soluble ion (basis of diffuse double layer theory; significant soil fertility variations compared with the untreated
Bohn et al., 1979). Consequently, multivalent cations were pref- soil. The treated Norfolk Ap soil pH was more basic after
erentially adsorbed over monovalent cations on exchange sites,
and hence, the monovalent K and Na cations would be more
available for movement with the leachate. TABLE 5. Changes in Norfolk Ap soil fertility characteristics
The decrease in concentration of multivalent cations in the with and without 2% biochar (after 67-day incubation and
two deionized water leaching events)
leachates with increasing levels of biochar addition (Table 4)
is particularity interesting in light of the fact that substantial 0% 2% Net Relative
amounts of Ca and Mg and less amounts of Mn and Zn were Characteristic Unit Biochar Biochar change %†
present in the biochar (Table 1). Much of the Ca added with
the biochar probably replaced monomeric Al species on clays pH V 4.8 6.4 +1.6 +33
and/or soil organic matter exchange sites [see Reaction (1)]. CEC cmolc kgj1 5.7 5.9 +0.2 +3.5
This hypothesis is supported by increasing levels of Mehlich Exchange cmolc kgj1 2.4 1.5 j0.9 +38
1Yextractable Ca with higher levels of biochar addition (Table 3). acidity
An explanation for the decrease in Mg, Mn, and Zn concentra- C g kgj1 17.4 29.2 +11.8 +68
tions in day-27 leachates is a bit more complex, because their Ca mg kgj1 437 692 +255 +58
Mehlich 1Yextractable concentrations of these elements either Cu mg kgj1 0.6 0.8 +0.2 +33
decreased or did not show substantial changes with increasing K mg kgj1 35 69 +37 +106
biochar additions. These observations suggest that the Mg, Mn, Mg mg kgj1 117 89 j28 j24
and Zn were either specifically adsorbed or very highly selec-
Mn mg kgj1 12 10 j2 j17
tively adsorbed by exchange sites associated with the biochar.
N g kgj1 1.24 1.21 j0.03 j2.4
The P concentrations generally decreased with increasing
biochar application in both 25- and 67-day leachates by approxi- Na mg kgj1 5 4 j1 j20
mately 40% (0 vs. 2% biochar addition; Table 4). The field from P mg kgj1 31 34 +3 +10
which the Norfolk soil was collected has a long history of row S mg kgj1 9 4 j5 j56
crop production; past P fertilizer applications were the likely Zn mg kgj1 13 10 j3 j23
source of much P in the soil. The declines in leachate P concen- †
Percent change based on values in Norfolk Ap soil + 0% biochar.
trations with increasing biochar additions are probably due to a
Copyright @ 2009 by Lippincott Williams & Wilkins. Unauthorized reproduction of this article is prohibited.
Soil Science & Volume 174, Number 2, February 2009 Biochar in Coastal Plain Soil
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http://pubs.usgs.gov/sir/5292 (verified November 6, 2008). Monitoring of nitrate leaching in sandy soils. J. Environ. Qual. 36:
Schmidt, M. W., and A. G. Noack. 2000. Black carbon in soils and sedi- 953Y962.
Copyright @ 2009 by Lippincott Williams & Wilkins. Unauthorized reproduction of this article is prohibited.
Poster Black carbon from rice residues as soil amendment and for carbon sequestration
identificat
ion card 1Haefele SM, 2Konboon Y, 3Knoblauch C, 4Koyama S, 1Gummert M, 1Ladha JK
1 International Rice Research Institute, 2 Ubon Ratchathani Rice Research Center, 3 University of Hamburg, 4 Japan International Cooperation Agency Tsukuba, INTERNATIONAL RICE RESEARCH INSTITUTE
IRRI
1 Background and objectives 3. The effect of carbonized rice husks in greenhouse and field experiments
On highly weathered soils in tropical and subtropical climates, maintenance of soil To investigate the effect of carbonized residue application, we conducted
organic matter is essential to sustain system productivity and avoid rapid soil greenhouse studies and established field experiments in different rice production
degradation. But climatic conditions as well as soil characteristics favor the rapid systems (irrigated and rainfed). Preliminary results indicate beneficial agronomic
decomposition of organic matter. However, several recent studies indicated that effects on poor soils only. Analysis of the effect on soil characteristics has not yet
carbonized plant residues (black carbon), the product of incomplete combustion of been completed.
organic material, could combine characteristics highly beneficial for soil nutrient
Greenhouse experiment
dynamics with high stability against chemical and microbial breakdown. Our ab
a
ab
project investigates i) past and present uses of carbonized rice residues, ii) the b
b
b
production under oxic conditions. Error bars indicate standard sequestration in the soil.
deviation of quadruplicate incubations, the diamond the
content of Corg in the different treatments. Presented by SM Haefele, IRRI
(shaefele@cgiar.org)
Conclusions:
Oxic
Preliminary results: If dried rice husks were added, the initial Carbonized crop residues could contribute to increase soil
CO2 and CH4 production rates increased by a factor of 3 to 7. carbon storage (carbon sequestration), reduce climate-relevant
In case of the addition of carbonized material, no effect could
No rice
husk
Carboni
zed rice
Untreat
ed rice
No rice
husk
Carboni
zed rice
Untreat
ed rice be measured. These results indicate the strong resistance of gas emissions and improve the natural soil resource in rice-
added husk
added
husk
added
added husk
added
husk
added carbonized organic matter towards microbial breakdown. based production systems.
Climate Change: Global Risks, Challenges and Decisions IOP Publishing
IOP Conf. Series: Earth and Environmental Science 6 (2009) 372052 doi:10.1088/1755-1307/6/7/372052
P37.45
Biochar as a soil amendment positively interacts with nitrogen fertiliser to improve barley yields in
the UK
Alfred Gathorne-Hardy, J Knight, J Woods
Imperial College, Centre for Energy Policy and Technology (ICEPT), London, UK
Introduction: Soil organic carbon (SOC) is vital for sustainable yields, retaining water and nutrients,
providing a habitat for soil biota and improving soil structure (Lorenz 2007). SOC is also a major carbon
store, containing over twice the total carbon present in the atmosphere. Land Use Change and arable
farming practises have already led to a marked reduction in SOC, and with the increased temperatures
expected with climate change SOC is likely to fall further (Raich, Potter et al. 2002). Its loss reduces soil
fertility and further exacerbates climate change.
Biochar, the use of charcoal as a soil amendment, has been proposed to increase both SOC levels and soil
fertility.
Biochar has two key properties:
1. a high affinity to nutrients and water, reducing onsite nutrient loss and offsite pollution from
nutrient leaching
2. a long residence time. Unlike soil amendments such as compost/manure biochar has a half life of
up to several centuries (Lehmann, Gaunt et al. 2006)
The long residence time has lead to biochar’s promotion for carbon sequestration, as it solves the lack of
permanence problem that plagues most other (non-geological) carbon capture and storage programmes, for
example afforestation. But before biochar can be widely taken up it is essential that its impacts on arable
cropping are understood. To date there has been almost no work looking at the use of biochar in temperate
agriculture.
Aim: To investigate the impacts of different rates of biochar on cereal growth within temperate agriculture,
and specifically the interaction of biochar and nitrogen fertiliser.
Methods: In 2008 a semi-randomised block design was established using spring barley on light land with
five levels of biochar (0, 5 10, 20 and 50 t/ha) and 5 levels of N (ammonium nitrate) fertiliser (0, 25, 50, 70
and 100 kgN/ha). Each biochar level was tested against each N level, giving 25 treatments. Each treatment
was repeated 5 times. Other nutrients were supersaturated on all plots. Results were analysed using
ANOVA in R.
Results and Conclusions: Interestingly the results showed no significant effect of yield for biochar alone, but
do show a significant interaction (p = 0.055) between biochar and N fertiliser. Biochar appears to increase
the nitrogen use efficiency. In this site the addition of 50t/ha of biochar increased the total yield by c. 30%
when high levels of N were used.
A likely explanation for the lack of effect from biochar alone on yield is that one of the most important
attributes of biochar – its ability to retain water – was not tested as the 2008 growing season was
exceptionally wet, so water was unlikely to have been a limiting factor.
c 2009 IOP Publishing Ltd 1
Climate Change: Global Risks, Challenges and Decisions IOP Publishing
IOP Conf. Series: Earth and Environmental Science 6 (2009) 372052 doi:10.1088/1755-1307/6/7/372052
250
Barley yield (g/250cm2)
200
0 N kg/ha
150
10 N kg/ha
100 20 N kg/ha
80 N kg/ha
50
100 N kg/ha
0
0 5 10 20 50
Biochar application rate (t/ha)
Figure 1. The effect of different levels of biochar, N fertiliser, and their interactions on barley yield
In addition to the onsite experiment, an economic model is being developed to see which price mechanisms,
if any, are required to encourage farmers to use biochar as a regular soil amendment.
Conclusion: These results demonstrate that biochar can have an important role in addressing climate change
through carbon sequestration and increased nitrogen use efficiency, and at the same time improving yields
and food security.
It is hoped that through its high affinity to nutrients and water biochar can help to buffer climatic variability
and reduce the need for fertiliser inputs. Thus biochar could both adapt agriculture to, and mitigate it from,
climate change.
List of References
Lehmann, J., J. Gaunt, et al. (2006). "Bio-Char Sequestration in Terrestrial Ecosystems – a Review." Mitigation and Adaptation
Strategies for Global Change 11: 25.
Lorenz, K. (2007). "Strengthening the soil organic carbon pool by increasing contributions from recalcitrant aliphatic
bio(macro)molecules." Geoderma 142(1-2): 1-10.
Raich, J. W., C. S. Potter, et al. (2002). Interannual variability in global soil respiration, 1980-94. 8: 800-812.
2
African Journal of Agricultural Research Vol. 3 (11), pp. 759-774, November, 2008
Available online at http://www.academicjournals.org/AJAR
ISSN 1991-637X © 2008 Academic Journals
Carbonized organic materials have not traditionally been applied to grain legumes such as soybean
(Glycine max L. Merrill) and cowpea (Vigna unguiculata L. Walp) although the potential for favourable
agronomic responses exist because of their high contents of available P. We explored the effects of
carbonized chicken manure and carbonized refuse derived fuel (RDF) from municipal organic waste
with or without inorganic K fertilization on the growth, nodulation, seed yield, N and P contents of
soybean and cowpea in a vinyl house pot experiment. Growth, nodulation, plant total N and P contents
were evaluated at peak flowering stage of legume growth. The application of carbonized chicken
manure only increased seed yield by 41 and 146% for soybean and cowpea respectively while the
carbonized chicken manure with inorganic K fertilizer increased seed yield by 53 and 185% for soybean
and cowpea respectively relative to the un-amended control. The application of carbonized RDF only
increased seed yield by 20 and 59% for soybean and cowpea respectively while the application of
carbonized RDF with inorganic K fertilizer increased seed yield by 45 and 126% for soybean and
cowpea respectively relative to the absolute control. The application of both carbonized organic
materials with inorganic K fertilizer increased number of nodules more than their sole application.
Results suggested that the application of carbonized chicken manure and carbonized RDF improved the
growth, nodulation, seed yield, N and P contents of both grain legumes due to their high content of P.
The application of the carbonized organic materials with inorganic K fertilizer further increased seed
yields of both grain legumes suggesting that K was limiting the response to P from the organic
materials in the experimental soil.
Key words: Carbonization, chicken manure, grain legumes, refuse derived fuel, seed yield.
INTRODUCTION
Soybean (Glycine max (L) Merrill) and Cowpea (Vigna in West Africa are N and P (Fox and Kang, 1977). The
unguiculata (L) Walp) are important grain legumes grown high cost and scarcity of inorganic fertilizers had renewed
in the tropics and sub-tropics. Cowpea is particularly interest in the use of unorthodox organic soil amendment
important in West Africa where it occupies 6 million materials such as carbonized organic materials (Shinogi
hectares of agricultural land (Bationo et al., 1990) with et al., 2003) and bio-char (Ishii and Kadoya, 1994) for
over 9.3 million metric tons of annual production (Ortiz, cultivation of crops.
1998). The main limiting nutrients for legume production Carbonization has been proposed as a management
tool for agricultural and municipal wastes producing
fertilizer, renewable energy and bio-char. Carbonization is
achieved through pyrolysis of organic wastes at tempera-
o
*Corresponding author. E-mail:sethtagoe@hotmail.com; tures ranging between 300 and 500 C and eliminates the
Tel: +81-90-1822-9702. Fax: +81-58-293-2846. bad smell, reduces the volume and weight of organic
wastes (Popov et al., 2004). During carbonization, some
760 Afr. J. Agric. Res.
amount of N is lost in the form of ammonia gas but the treatments three weeks before sowing. Potassium fertilizer was
resulting carbonized material is higher in available P by applied as Muriate of Potash (KCl) at a rate of 83 kg K ha-1 to the
appropriate treatments at sowing. No chemical pesticides were
up to 5 times compared to the original waste (Shinogi et used in this experiment. Five seeds of soybean (Glycine max (L)
al., 2003; Tagoe et al., 2008). Merrill cv Akishirome) and cowpea (V. unguiculata (L) Walp cv
Carbonized organic wastes can be used as soil Tsurushi sasage) were sown per pot on 7th June, 2007. After
amendments to supply plant nutrients especially N and P. emergence, seedlings were thinned to two per pot. Plants were
The application of carbonized organic wastes to soil watered as when necessary. All pots were kept completely free of
improve the physical properties of the soil, improve soil weeds within the duration of the experiment by hand-picking when
they appear.
fertility and nutrient retention (Sombroek et al., 1993;
Lehmann and Rondon., 2005), stimulate microbial
Experimental design
activities in soil (Tejada et al., 2006), increase mycorrhizal
abundance and/or functioning (Warnock et al., 2007), The experiment was set up using two grain legumes (soybean and
increase nodule abundance in soybean (Tagoe et al., cowpea), two carbonized organic materials (carbonized chicken
2008) as well as improve biological N2 fixation in common manure and carbonized RDF) with two rates of inorganic K fertilizer
with or without K, 83 kg K ha-1 and 0 kg K ha-1 respectively in a
beans (Rondon et al., 2007). factorial combination giving a total of 48 treatments (2 x 2 x 2 x 6)
No work has been reported in the scientific literature on arranged in completely randomized design (CRD) of six
the use of carbonized refuse derived fuel (CRDF) as soil replications. All data collected from the study were analyzed by
amendment for legume growth while only one work had using Duncan’s Multiple Range Test (DMRT) (Excel Statistical
been reported on the use of carbonized chicken manure Package Version 6.0) and mean separations were done by the
as soil amendment for soybean growth (Tagoe et al., same method.
2008). In this study, we assess the effects of two
carbonized organic soil amendment materials (chicken Measurements
manure and RDF) on the growth, nodulation, yield, N and Plant height and relative chlorophyll content (SPAD) were
P concentrations of two grain legumes (soybean and measured twice within the duration of the experiment. For both
cowpea) with or without inorganic K fertilizer. We parameters, the first (pre-flowering) and second (post-flowering)
hypothesized that the application of carbonized organic samplings were done on 16th July and 31st July respectively. SPAD
materials will improve the growth, nodulation, seed yield, was measured with a chlorophyll meter model SPAD-502 (Minolta
N and P concentrations of grain legumes more with K Co. Ltd., Japan). SPAD readings were taken from 12 randomly
selected youngest and fully expanded leaves of plants in each pot.
fertilizer than without K fertilizer because K could limit the Each SPAD reading was taken on one side of the mid-rib of the leaf
response of grain legumes to P from carbonized organic blade, midway between the leaf blade and tip.
materials in low P status soils (Carsky, 2003) and also Sampling for leaf area, dry matter weight, and number of nodules
because of the low K content of the experimental soil. was done on 26th July for cowpea and 1st August for soybean
Our major objectives are to elucidate the effect of when the plants were at peak flowering stage. Shoots were
harvested by cutting the plants in each pot at the soil level. Roots
carbonized chicken manure and carbonized RDF on 1)
were harvested by lifting the soil in each pot and washing off the
the growth, nodulation and seed yield and 2) plant and soil under running water from a tap. The harvested shoots were
seed concentrations of N and P of both crops. separated into leaves, stems (including petioles), flowers etc. The
roots were washed clean of soil and root nodules were separated
and counted. The leaves were used to estimate leaf area by the
MATERIALS AND METHODS core borer method after oven-drying harvested samples at 80oC for
72 h. The dried samples were then weighed to determine dry
Plant culture weights of leaves, stems, roots and nodules and finally total dry
matter weight.
Experiments were conducted from May to October, 2007 at the The total dry material was milled to pass 0.5 mm mesh sieve
greenhouse of Gifu University Experiment Farm (35o 27’ N, 136o 46’ using a wonder blender (Model WB-1). The milled plant samples
E). Wagner pots (1/2000a) were filled with sandy loam soil with the were used for total N and total P analyses and determination. Total
following characteristics: pH; 5.62, EC; 0.28 mS cm-1, total N; N was determined with an automatic high sensitive NC analyzer
0.100%, total C; 0.88%, available P; 1.16 mg 100 g-1, available K; (Sumigraph NC-95A, Shimadzu Co. Ltd., Japan). Total P was
13.3 mg 100 g-1, available Ca; 90.0 mg 100 g-1, and available Mg; determined colorimetrically (HITACHI-U-1800) according to Bray
31.0 mg 100 g-1. The nutrient concentrations, pH and EC of the and Kurtz (1945) and Murphy and Riley (1962).
carbonized chicken manure and RDF used in the experiment are Residual experimental soil exchangeable cations (K+, Ca2+, and
shown in Table 1. Carbonized chicken manure was obtained from Mg2+) were measured with a Polarized Zeeman Atomic Absorption
Tokyo Yougyou Kabushiki Kaisha, Tajimi City, Gifu Prefecture, Spectrophotometer (HITACHI-180-60) after extraction of samples
Japan. Carbonized chicken manure was produced from pelleted, with 1.0N Ammonium acetate solution (pH 7.0).
dried chicken manure through pyrolysis at a temperature of 450oC
for one hour in a furnace. Carbonized RDF was obtained from
Kurimoto Tekkosho, In a City, Gifu Prefecture, Japan. Carbonized RESULTS
RDF was prepared from municipal organic waste through pyrolysis
at a temperature of 500oC for 2 h in a kiln after drying the waste in a Plant growth
furnace for 10 h. The amounts of the carbonized organic materials
applied per pot for the various treatments are shown in Table 2.
Carbonized organic amendments were applied to the appropriate
At the pre-flowering sampling of the relative chlorophyll
Tagoe et al. 761
Table 1. Nutrient composition of carbonized organic materials used in the experiment after pyrolysis.
† The pH and EC were measured in the extracts of carbonized organic materials in distilled water
[ 1:20 (w/v)] on dry weight basis.
Table 2. Treatment details showing amounts of carbonized organic materials and inorganic K fertilizer applied per pot and treatment
abbreviations.
content (SPAD) leaves of soybean plants treated with Leaves of control cowpea plants that received K fertilizer
carbonized chicken manure were the greenest. Leaves of were greener than those that did not (Figure 2). At the
soybean plants treated with carbonized RDF were of post-flowering sampling of SPAD for cowpea, a similar
intermediate greenness while those of the control were trend to the pre-flowering SPAD was observed except
the least green with or without K fertilizer. Generally, that leaves of control cowpea plants without K fertilizer
leaves of soybean plants without K fertilizer were greener were greener than those with K fertilizer (Figure 2). The
than those with K fertilizer (Figure 1). The observed observed differences among treatments for both pre-
differences were significant according to DMRT at p< flowering and post-flowering were significant at p<0.05
0.05. according to DMRT.
At the post-flowering sampling of SPAD, a similar trend Total dry weight was significantly highest according to
was observed for the control and carbonized RDF DMRT at p<0.05 in soybean plants treated with
treatments with or without K fertilizer. However, leaves of carbonized chicken manure followed by those treated
soybean plants treated with carbonized chicken manure with carbonized RDF. Control soybean plants were least
were the greenest with or without K fertilizer (Figure 1). At heavy in total dry weight (Table 3). For all treatments,
the pre-flowering sampling of SPAD of cowpea, leaves of soybean plants with K fertilization produced heavier dry
plants treated with carbonized chicken manure with or matter than the corresponding treatments without K
without K fertilizer were the greenest. Cowpea leaves of fertilization (Table 3). There was a strong and significant
plants treated with carbonized RDF with or without K positive relationship between total dry weight and plant
2
fertilizer were of intermediate greenness. Leaves of total N content of soybean (R = 0.79 **, Figure 3a). A
cowpea plants without any organic amendment (control) strong and significant positive relationship was observed
with or without K fertilizer were least green (Figure 2). For between soybean total dry weight and plant total P
2
cowpea leaves of plants treated with carbonized chicken content (R = 0.90 **, Figure 3b).
manure and carbonized RDF, no difference in greenness Total dry weight of cowpea followed a similar trend as
were observed for treatments with and without K fertilizer. that of soybean. Cowpea plants treated with carbonized
762 Afr. J. Agric. Res.
Figure 1. Effects of carbonized organic materials supply on the pre-flowering and post-flowering
SPAD values of soybean. Data show the means ± SD of three independent replications.
Figure 2. Effects of carbonized organic materials supply on the pre-flowering and post-flowering
SPAD values of cowpea. Data show the means ± SD of three independent replications.
chicken manure produced significantly the highest dry produced the least dry matter (Table 4). For all
matter followed by those treated with carbonized RDF treatments, cowpea plants that received K fertilizer
according to DMRT at p<0.05. Control cowpea plants produced heavier dry matter than those that did not
Tagoe et al. 763
Table 3. Growth, nodulation, total N and P contents of soybean as affected by the application of carbonized organic materials.
Treatment K fertilizer Total dry Number of Plant total N Seed total N Plant total P Seed total P
weight (g) nodules content (g content (g content (g content (g
kg-1) kg-1) kg-1) kg-1)
Control Without K 38.0 a 380.7 a 27.8 a 66.1 a 0.35 a 0.09 a
With K 49.3 b 428.3 b 27.2 a 66.8 a 0.38 b 0.11 b
CCM Without K 64.2 c 529.3 c 31.9 c 72.8 d 0.44 d 0.27 c
With K 81.8 d 611.0 d 33.0 d 73.8 e 0.47 f 0.34 e
CRDF Without K 54.1 b 437.3 b 30.4 b 70.8 b 0.43 c 0.26 c
With K 69.2 c 567.0 c 30.8 b 71.8 c 0.45 e 0.31 d
Within each column, means having a common letter(s) are not significantly different according to DMRT at p < 0.05.
Table 4. Total dry weight, number of nodules, total N and P contents of cowpea as affected by the application of carbonized
organic materials.
Treatment K fertilizer Total dry Number of Plant total Seed total Plant total Seed total
weight (g) nodules N content N content P content P content
(g kg-1) (g kg-1) (g kg-1) (g kg-1)
Control Without K 17.5 a 103.3 a 23.1 a 40.3 a 0.54 a 0.12 a
With K 31.7 bc 140.0 b 22.9 a 41.3 b 0.56 b 0.14 b
CCM Without K 34.8 c 122.0 ab 27.3 c 46.6 e 0.64 d 0.18 d
With K 38.3 d 215.0 d 31.9 d 47.9 f 0.67 e 0.21 f
CRDF Without K 29.3 b 113.0 a 24.9 b 43.5 c 0.62 c 0.16 c
With K 37.7 d 189.0 c 28.0 c 44.9 d 0.64 d 0.19 e
Within each column, means having a common letter(s) are not significantly different according to DMRT at p < 0.05.
(Table 4).There was a significant positive relationship nodules (Table 4). There was a significant positive
between total dry weight and plant total N content of relationship between number of nodules and plant total N
2 2
cowpea (R = 0.56 *, Figure 4a). A strong and significant content of cowpea (R = 0.68 *, Figure 6a). No significant
positive relationship was observed between total dry positive relationship was observed between number of
2 2
weight and plant total P content of cowpea (R = 0.70 **, nodules and plant total P content of cowpea (R = 0.43
Figure 4b). ns, Figure 6b).
Number of nodules of soybean was significantly highest
in soybean plants treated with carbonized chicken
manure followed by those treated with carbonized RDF Yield and yield components
according to DMRT at p<0.05. Control soybean plants
produced the least number of nodules. For each Dry pod yield and seed yield of soybean followed a
carbonized organic amendment treatment, soybean similar trend. Soybean seed yield was heaviest in
plants that received K fertilizer produced more nodules treatments amended with carbonized chicken manure
than those that did not (Table 3). There was a strong and with or without K fertilizer followed by carbonized RDF
significant positive relationship between number of amended treatments with or without K fertilizer. Soybean
2
nodules and plant total N content of soybean (R = seed yield was least in control treatments with or without
0.75**, Figure 5a). Also, a strong and significant positive K fertilizer (Table 5). Generally, carbonized organic
relationship was observed between number of nodules amendment treatments that received K fertilizer produced
2
and plant total P content of soybean (R = 0.83**, Figure better dry pod and seed yields than those without K
5b). fertilizer. The application of carbonized chicken manure
Cowpea plants of both carbonized organic amendment only increased soybean seed yield by 41% while the
treatments without K fertilization produced similar number application of carbonized RDF only increased soybean
of nodules. However, cowpea plants treated with seed yield by 20%. The application of carbonized chicken
carbonized chicken manure and K fertilizer produced manure and K fertilizer increased soybean seed yield by
significantly the greatest number of nodules followed by 53% while the application of carbonized RDF and K
cowpea plants treated with carbonized RDF and K fertilizer increased soybean seed yield by 45%.
fertilizer according to DMRT at p<0.05. Control cowpea Dry pod yield and seed yield of cowpea followed a
plants with K fertilizer produced the least number of similar trend. Cowpea plants treated with carbonized
764 Afr. J. Agric. Res.
Figure 3. Relationship between total dry weight, plant total N content and plant total P content of soybean
at peak flowering.
3a. Relationship between total dry weight and plant total N content of soybean at peak flowering stag
3b. Relationship between total dry weight and plant total P content of soybean at peak flowering stage
Tagoe et al. 765
Figure 4. Relationship between total dry weight, plant total N content and plant total P content of cowpea
at peak flowering.
4a. Relationship between total dry weight and plant total N content of cowpea at peak flowering stage.
4b. Relationship between total dry weight and plant total P content of cowpea at peak flowering stage.
766 Afr. J. Agric. Res.
Figure 5. Relationship between number of nodules, plant total N content and plant total P content of soybean at
peak flowering.
5a. Relationship between number of nodules and plant total N content of soybean at peak flowering stage.
5b. Relationship between number of nodules and plant total P content of soybean at peak flowering stage.
Tagoe et al. 767
(6a)
6b)
Figure 6. Relationship between number of nodules, plant total N content and plant total P content of cowpea at peak
flowering.
6a. Relationship between number of nodules and plant total N content of cowpea at peak flowering stage.
6b. Relationship between number of nodules and plant total P content of cowpea at peak flowering stage.
768 Afr. J. Agric. Res.
Table 5. Yield and yield components of soybean as affected by the application of carbonized organic materials.
Treatment K fertilizer Dry pod Seed yield No. of No. of 100 seed Harvest
yield (g) (g) pods seeds wt (g) index
plant-1 pod-1
Control Without K 49.5 a 38.1 a 50.4 a 1.8 a 26.4 a 0.54 ab
With K 68.7 c 52.9 c 108.7 c 1.8 a 28.0 b 0.63 e
CCM Without K 69.8 c 53.7 c 79.0 c 1.9 b 28.9 c 0.57 bc
With K 71.9 cd 58.4 d 137.5 d 2.0 c 29.9 e 0.59 bc
CRDF Without K 59.7 b 45.9 b 68.9 b 1.9 b 27.8 b 0.67 e
With K 75.8 d 55.4 cd 103.7 d 1.9 b 29.6 d 0.52 a
Table 6. Yield and yield components of cowpea as affected by the application of carbonized organic materials.
Treatment K fertilizer Dry pod Seed yield No. of pods No. of 100 seed Harvest
yield (g) (g) plant-1 seeds pod-1 wt (g) index
Control Without K 26.1 a 14.2 a 9.4 a 11.7 ab 17.4 a 0.66 d
With K 40.6 c 27.6 c 12.0 bc 11.3 ab 17.3 a 0.60 ab
CCM Without K 47,9 d 34.9 e 11.9 b 12.0 b 19.8 b 0.61 bc
With K 54.9 e 40.5 f 14.9 d 12.3 b 20.2 b 0.63 c
CRDF Without K 35.6 b 22.6 b 11.4 b 10.7 a 18.1 a 0.59 ab
With K 47.1 d 32.1 d 13.0 c 11.3 ab 19.6 b 0.58 a
chicken manure with or without K fertilizer produced the in all organic amendment treatments. 100 seed weight
heaviest seed yield followed by those treated with was significantly heaviest in carbonized chicken manure
carbonized RDF. Control cowpea plants with or without K treated plants according to DMRT at p< 0.05 followed by
fertilizer produced the least heavy seed yield. Generally, carbonized RDF treated plants. 100 seed weight was
cowpea plants that received K fertilizer produced heavier least heavy in control soybean plants (Table 5).
seed yield than those that did not receive K fertilizer 100 seed weight of cowpea was not affected by K
(Table 6). Cowpea seed yield increased 146% by the fertilizer application in control and carbonized chicken
application of carbonized chicken manure only while it manure treated plants but was increased slightly in
increased by 49% as a result of the application of carbonized RDF treated plants. 100 seed weight of
carbonized RDF only. The application of carbonized cowpea was highest in plants treated with carbonized
chicken manure and K fertilizer increased cowpea seed chicken manure with or without K fertilizer and similar to
yield by 185% while the application of carbonized RDF plants treated with carbonized RDF and K fertilizer (Table
and K fertilizer increased it by 126%. 6).
Number of pods/plant of soybean followed a similar Harvest index was increased by K fertilizer application
pattern to dry pod and seed yields of soybean. In all in control soybean plants and reduced in carbonized RDF
treatments, number of pods/plant of soybean was better treated soybean plants. K fertilizer application did not
for treatments that received K fertilizer than for those affect harvest index in carbonized chicken manure
without K fertilizer (Table 5). treated soybean plants (Table 5).
Number of pods/plant was highest in cowpea plants that Harvest index of cowpea did not follow any particular
received K fertilizer than those that did not for all trend but was highest in control cowpea plants without K
treatments. Number of pods/plant was significantly fertilizer and lowest in carbonized RDF treated plants with
highest in cowpea plants treated with carbonized chicken K fertilizer (Table 6).
manure followed by carbonized RDF. Number of
pods/plant was least in control cowpea plants.
Number of seeds per pod was only slightly increased by
K fertilizer in soybean plants treated with carbonized N contents
chicken manure (Table 5).
Number of seeds/pod of cowpea was neither affected Plant total N content of soybean was highest in
by carbonized organic amendment material supply nor K carbonized chicken manure amended plants followed by
fertilizer application (Table 6). carbonized RDF amended plants. Control soybean plants
100 seed weight of soybean was increased by K fertilizer were least in plant total N content (Table 3). K fertilizer
Tagoe et al. 769
2
only slightly increased plant total N content of carbonized of cowpea (R = 0.83**, Figure 10).
chicken manure amended soybean plants while it had no
effect on plant total N content of carbonized RDF
amended soybean plants (Table 3). Seed total N content DISCUSSION
of soybean followed a similar trend as plant total N
content of soybean. The only difference is that K fertilizer The effects of two carbonized organic materials that is,
application increased seed total N content of carbonized chicken manure and refuse derived fuel (RDF) with or
chicken manure and carbonized RDF amended soybean without inorganic K fertilizer on the growth, nodulation,
plants while it had no effect on seed total N content of yield, N and P contents of two grain legumes i.e. soybean
control soybean plants (Table 3). There was a significant and cowpea were explored in this greenhouse trial. The
positive relationship between seed total N content and application of carbonized chicken manure only increased
2
seed yield of soybean (R = 0.50*, Figure 7). seed yield by 41 and 146% in soybean and cowpea
Plant total N content of cowpea was highest in plants respectively while the application of carbonized chicken
treated with carbonized chicken manure with or without K manure and inorganic K fertilizer increased seed yield by
fertilizer followed by plants treated with carbonized RDF 53 and 185% in soybean and cowpea respectively. The
with or without K fertilizer. Control cowpea plants were application of carbonized RDF only increased seed yield
lowest in plant total N content with or without K fertilizer by 20 and 59% in soybean and cowpea respectively
(Table 4). K fertilizer application increased plant total N while the application of carbonized RDF and inorganic K
content in carbonized chicken manure and carbonized fertilizer increased seed yield by 45 and 126% in soybean
RDF amended cowpea plants but not in control cowpea and cowpea respectively. The trends for dry pod yield and
plants (Table 4). Seed total N content of cowpea followed total dry weight of both grain legumes were similar to that
a similar trend (Table 4). However, K fertilizer application of their respective seed yields. This result is consistent
increased cowpea seed total N content in all treatments with that reported by Rondon et al. (2007) who observed
(Table 4). There was a strong positive relationship a 46% increase in common bean yield over the control in
between plant total N content and seed yield of cowpea response to bio-char application. Chan et al. (2007)
2
(R = 0.72**) as well as between seed total N content and observed in their work that in the absence of N fertilizer,
2
seed yield of cowpea (R = 0.81**, Figure 8). green-waste bio-char application to soil did not increase
radish yield even at higher rates but reported significant
bio-char and N fertilizer interaction highlighting the role of
P contents bio-char in improving N fertilizer use efficiency of the
plant. Although few works are available for comparison
Plant total P content of soybean was affected by both with the results of this study, our results are consistent
carbonized organic amendment supply and K fertilizer with previous works done using ordinary un-carbonized
application. Plant total P content of soybean was highest chicken manure. Garcia and Blancaver (1983) reported
in plants amended with carbonized chicken manure with that the application of poultry manure increased soybean
or without K fertilizer followed by carbonized RDF treated seed yield by 62% over the control. Schmidt et al. (2001)
plants with or without K fertilizer. Control soybean plants found that soybean seed yield increased linearly with
were lowest in plant total P content (Table 3). K fertilizer increasing swine manure rate. Several researchers have
application increased plant total P contents of all reported soybean seed yield increases with applied
treatments (Table 3). Seed total P content of soybean commercial N fertilizer (Lamb et al., 1990; Wesley et al.,
followed a similar trend as plant total P content of 1998). The higher seed yields of both grain legumes in
soybean (Table 3). There was a positive relationship response to the application of carbonized organic
between plant total P content and seed yield of soybean materials especially carbonized chicken manure suggest
2
(R = 0.62*, Figure 9). that both N and P are important nutrients that influence
Plant total P content of cowpea was affected by both the growth and yield of soybean and cowpea. Carbonized
carbonized organic amendment and K fertilizer chicken manure and carbonized RDF contain high levels
application. Plant total P content of cowpea was highest of macro-nutrients especially N and P as well as micro-
in carbonized chicken manure amended cowpea plants nutrients that would be available to plant roots and soil
with or without K fertilizer followed by carbonized RDF biota. Hariston et al. (1990) and Schmidt et al. (2001)
amended plants with or without K fertilizer. Plant total P observed that soybean not only requires a considerable
content was lowest in control cowpea plants (Table 4). K amount of N to produce a crop, but also a constant
fertilizer application increased plant total P contents of supply of available P to maintain rapid growth and
cowpea in all treatments. Seed total P content of cowpea development. Carbonized chicken manure and
followed a similar trend as plant total P content of cowpea carbonized RDF are particularly rich in both total and
(Table 4). There was a strong positive relationship available P and their application to soil at high rates can
between plant total P content and seed yield of cowpea supply a considerable amount of available P for plant
2
(R = 0.71**, Figure 10). There was a strong positive uptake. Again, carbonized organic materials such as
relationship between seed total P content and seed yield
770 Afr. J. Agric. Res.
Figure 8. Relationship between plant total N content, seed total N content and seed yield of cowpea.
carbonized chicken manure, carbonized RDF and bio- retaining nutrients and improving soil physical and
char can act as soil conditioners to enhance plant growth biological properties (Glaser et al., 2002; Lehmann and
by supplying macro and micro-nutrient elements, Randon, 2005). Abdelhamid et al. (2004) found increased
Tagoe et al. 771
Figure 10. Relationship between plant total P content, seed total P content and seed yield of cowpea.
772 Afr. J. Agric. Res.
dry weight of faba bean as a result of chicken manure plays important roles in establishment, growth and
supply. Cowpea responded positively to the application of function of nodules (Israel, 1987; Beck and Munns, 1984;
carbonized chicken manure and CRDF in this study in Leung and Bottomley, 1987) and growth of host plants
terms of growth parameters and seed yield. This (Munns et al., 1981). Number of nodules is important
response underscores the importance of P as a critical because a positive correlation has been reported
nutrient element influencing the performance of cowpea between nodule number and total nitrogenase activity of
and soybean. Several researchers have reported soybean (Singleton and Bohlool, 1984) and alfalfa
significant responses of cowpea and soybean to P (Porter, 1983).
application (Tenebe et al., 1995; Ankomah et al., 1995; According to Gates and Muller (1979) the application of
Okeleye and Okelana, 1997). They observed significant fertilizer containing N, P and S to soybean contributed to
increases in total dry matter yield, number of flowers, pod forming a stronger symbiotic mechanism and more active
and seeds per plant, seed yield and nodulation as a N2-fixation. Since the carbonized organic materials used
result of P application. Rondon et al. (2007) reported a in this experiment especially carbonized chicken manure
39% increase in biomass production of common bean in contain N, P and S (Sharpley et al., 1993) their
response to bio-char application which they attributed to application to soybean and cowpea could be beneficial to
greater availability of K, Ca and P. Chan et al. (2007) the symbiotic N2-fixing mechanism. Low P availability is
observed additional increase in dry matter of radish in the especially problematic for leguminous crops because
presence of N fertilizer varied from 95% in the control to legume nodules responsible for N2-fixation have high P
266% in the 100 t/ha bio-char amended soils. Carsky requirement (Vance, 2001). P is essential for plant
(2003) working on the response of cowpea and soybean growth, nodulation and N2-fixation (Pereira and Bliss,
to P and K on terre de barre soils in southern Benin, 1989). Nodule number as well as nodule dry weight is
reported that soybean and cowpea grain yield increased greatly reduced by P deficiency (Ribet and Drevon, 1995)
by 147% and 95% respectively in response to P and nitrogenase activity varies with P availability (Israel,
application. 1987). Acute P deficiency is known to prevent nodulation
Number of nodules of soybean and cowpea increased of grain legumes. P deficiency is more likely to affect N2-
with the application of carbonized organic materials. This fixation legumes than other species because symbiotic
observation is consistent with that of Tagoe et al. (2008) N2-fixation is an energetically expensive process which
who reported increased nodule abundance of soybean as requires more P than does plant growth (Olivera et al.,
a result of carbonized chicken manure application and 2004). The strong positive relationship between number
attributed it to the high available P content of carbonized of nodules and plant total P content of soybean confirms
chicken manure. The application of carbonized chicken the importance of P in legume nodulation.
manure increased nodule abundance of both grain Total N and total P contents of plant and seed of
legumes more than carbonized RDF. This observation soybean and cowpea increased with the application of
can be attributed to the high P content of carbonized carbonized organic materials with or without inorganic K
chicken manure relative to carbonized RDF. Rondon et fertilizer. This observation is consistent with that reported
al. (2007) also observed that biological N2 fixation of by Jassen (1998) that nutrient uptake requires N, P and K
common bean increased with bio-char application. They in balance to reach maximum values. Adeli (2005)
reported that the proportion of fixed N increased from observed increased N concentration in the above ground
50% without bio-char addition to 72% with 90 g kg-1 bio- biomass of soybean in response to poultry manure
char added and attributed this observation to greater application. The application of chicken manure to faba
availability of B, and Mo and to a lesser extent K, Ca and bean increased total N contents in roots, shoots and the
P availability. The application of the carbonized organic whole plant (Abdelhamid et al., 2004). Belle (2006)
materials plus K fertilizer further increased the number of reported significant increases in the uptake of N and P in
nodules of both legumes thus confirming the hypothesis common bean as a result of the application of N and P
that K could limit the response of P from the carbonized fertilizers. Barker and Sawyer (2005) observed that N
organic materials in low P status soils (Carsky, 2003). P concentration in plant dry matter of soybean was
fertilization has been shown to increase number of increased significantly with applied N. Studies with
nodules and their weight in soybean (Cassman et al., several legumes have consistently shown a positive
1993; Jones et al., 1977) and in cowpea (Wan Othman et response to P application; whole plant N concentration
al., 1991). This is because P is known to initiate nodule and plant dry matter were found to increase in response
formation, increases the number of nodule primordia and to phosphate in the growth media (Pereira and Bliss,
is essential for the development and functioning of 1987). P application has been reported to influence the
formed nodules (Waluyo et al., 2004). Nodules are known contents of other nutrients in cowpea leaves (Kang and
to be a strong sink for P and P concentration in nodules Nangju, 1983), shoots (Bagayoko et al., 2000) and seed
can be three times higher than in other plant organs with (Omueti and Oyenuga, 1970). Seed total N content of
a minimum effect from P deficiency (Vadez et al., 1999). soybean was positively correlated with seed yield. Also
Several researchers have reported that the supply of P plant total N and seed total N contents of cowpea were
Tagoe et al. 773
correlated with seed yield of cowpea. These observations Bagayoko EG, Romheld V, Buerkert A (2000). Effects of mycorrhizae
and phosphorus on the growth and nutrient uptake of millet, cowpea
suggest the importance of N in the seed yields of these
and sorghum on a West African soil. J. Agric. Sci. Cambridge
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seeds especially soybean. Plant total P content of Bationo A, Mughogho SK, Mokwunye AU (1990). Agronomic evaluation
soybean was positively correlated with soybean seed of phosphate fertilizer in tropical Africa. In : Management of Nitrogen
and Phosphorus Fertilizers of Sub-saharan Africa (eds A.U.
yield. Also, plant total P and seed total P contents were
Mokwunye & P.L.G. Vlek) Dordrecht, The Netherlands, Martinus
positively correlated with seed yield in cowpea. These Nijhoff, pp. 283-318.
observations underscore the importance of not only N, Barker DW, Sawyer JE (2005). Nitrogen application to soybean at early
but P as well in increasing the growth and seed yield of reproductive development. Agron. J. 97:615-619.
Beck DP, Munns DN (1984). Phosphate nutrition of Rhizobium sp. Appl
these grain legumes. Environ Microbiol 47:278-282.
Bio-char addition can result in elevated quantities of Belle JO (2006). Effect of nitrogen and phosphorus fertilizers on seed
bio-available nutrients such as N, P and metal ions, in the quality and yield of common beans (Phaseolus vulgaris L.). 18th
soil (Tryon, 1948; Lehmann et al., 2003; Gundale and World Congress of Soil Science, July 9-15, 2006, Philadelphia,
Pennsylvania, USA.
DeLuca, 2006; DeLuca et al., 2006). Addition of bio-char
Bray RH, Kurtz LT (1945). Determination of total organic and available
to soil alters important soil physical and chemical forms of phosphorus in soils. Soil Sci. 59:39-45.
properties such as pH (Lucas and Davis, 1961) and Carsky RJ (2003). Response of cowpea and soybean to P and K on
typically increase soil cation exchange capacity (CEC) terre de barre soils in southern Benin. Agric. Ecosyst. Environ. 100:
241-249.
(Glaser et al., 2002), and can lead to greater water
Cassman KG, Singleton PW, Linguist BA (1993). Input/output analysis
holding capacity (WHC) while generally decreasing bulk of the cumulative soybean response to phosphorus on an Ultisol.
density (Tryon, 1948) as well as increase bio-available P Field Crops Res. 34: 23-26.
and cations in soils. Improvement in physical properties Chan KY, Van Zwieten L, Meszaros I, Downie A, Joseph S (2007).
Agronomic values of green-waste bio-char as soil amendment. Astral
of the soil as a result of the addition of carbonized J. Soil Res. 45(8): 629-634.
chicken manure and carbonized RDF to a lesser extent, DeLuca TH, MacKenzie MD, Gundale MJ, Holben WE (2006). Wildfire –
may have contributed to the increased growth and yield produced charcoal directly influences nitrogen cycling in ponderosa
of the grain legumes. pine forests. Soil Sci. Soc. Am. J. 70: 448-453.
Fox RL, Kang BT (1977). Exploiting the legume-rhizobium symbiosis in
Tropical Agriculture. In: University of Hawaii Publication No. 145 (eds
JM. Vincent, AS. Whitney, J Bose) pp. 183-210.
Conclusion Garcia JM, Blancaver AT (1983). Effect of animal manure on the growth
and yield of soybean and physical properties of the soil. J. Agric.
Food Nutr. 4:196-212.
The growth, nodulation, seed yield, total N and P
Gates CT, Muller WJ (1979). Nodule and plant development in the
contents of plant and seed of soybean and cowpea all soybean: Growth response to nitrogen, phosphorus and sulfur. Aust.
increased with the supply of carbonized chicken manure J Bot. 27: 203-215.
and carbonized RDF due to their high available P Glaser B, Lehmann J, Zech W (2002.). Ameliorating physical and
chemical properties of highly weathered soils in the tropics with
contents. The application of carbonized organic materials charcoal- a review. Biol. Fertil. Soils 35: 219-230.
and inorganic K fertilizer increased grain yield and other Gundale MJ, DeLuca TH (2006). Temperature and source material
parameters in both crops more than the sole application influence ecological attributes of Ponderosa pine and Douglas-fir
of the carbonized organic materials thus suggesting that charcoal. For Ecol Manag 231: 86-93.
Hariston JE, Jones WF, Marshall LK, Gill KB (1990). Tillage and fertilizer
it is a good potential option to be evaluated for use in the management effects on soybean growth and yield on three
field and home garden for grain legume production. Mississippi Soils. J Prod Agric 3: 317-323.
Ishii T, Kadoya K (1994). Effects of charcoal as a soil conditioner on
citrus growth and vesicular-arbuscular mycorrhizal development. J.
Jpn Soc. Hort. Sci. 63: 529-535.
ACKNOWLEDGEMENT
Israel DW (1987). Investigation of the role of phosphorus in symbiotic
nitrogen fixation. Plant Physiol 84:835-840.
The authors would like to express their profound gratitude Jassen BH (1998). Efficient use of nutrients: an art of balancing. Field
to the Ministry of Education, Culture, Sports, Science and Crops Res. 56: 197-201.
Jones GD, Lutz Jr. JA, Smith TJ (1977). Effects of phosphorus and
Technology, Japan for financial support without which this
potassium on soybean nodules and seed yield. Agron. J. 69:1003-
research would not have been possible. 1008.
Kang BT, Nangju D (1983). Phosphorus response to cowpea (Vigna
unguiculata L. Walp). Trop. Grain Legume Bul. 27: 11-16.
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Soil Science and Plant Nutrition (2006) 52, 489–495 doi: 10.1111/j.1747-0765.2006.00065.x
ORIGINAL ARTICLE
Effect
M. Yamato
of charcoal
Blackwell et al. application
Publishing, Ltd. on crop yield
Abstract
Charred bark of Acacia mangium (bark charcoal), which is made of wood waste from pulp production,
was applied as soil amendment for the cultivation of maize, cowpea and peanut to examine its effects on
crop yield and soil chemical properties in South Sumatra, Indonesia. The yields of maize and peanut signifi-
cantly increased after the application of bark charcoal under a fertilized condition in an infertile soil
environment. In addition, increases in the root amount and colonization rate of arbuscular mycorrhizal
(AM) fungi after bark charcoal application were also observed in maize. In general, the application of bark
charcoal induced changes in soil chemical properties by increasing the pH value, total N and available P2O5
contents, cation exchange capacity, amounts of exchangeable cations and base saturation, and by decreas-
ing the content of exchangeable Al3+. The amelioration of the soil chemical properties could be effective in
highly weathered infertile tropical soils. The application of charcoal in agriculture is expected to lead to
the formation of a carbon sink in soil and to increase crop yield because it has been suggested that charcoal
is highly resistant to abiotic and biotic degradation, even in a soil environment.
Key words: Arachis hypogaea L., arbuscular mycorrhizal fungi, bark charcoal, Vigna unguiculata L., Zea mays L.
each treatment, three ridges measuring 1 m × 2 m in size ridge after harvest, which were mixed together at each
were prepared and the applied chemical fertilizer and experimental site or in each treatment.
bark charcoal were mixed with topsoil at a depth of For each of the collected soil samples, the chemical
approximately 10 cm. The number and size of the pre- properties, pH (H2O), pH (KCl), amount of available
pared ridges for each treatment, the method of applica- P2O5 (Bray 1), CEC, amounts of exchangeable cations
tion of the chemical fertilizer and bark charcoal, the (K +, Na +, Ca 2+ and Mg 2+) and exchangeable acidity
seed sowing position and the number of plants were the (Al3+ and H+) were determined. The analytical methods
same as those described for maize in Experiment 1. were the same as those described above for the charcoal
The seeds were sown on 12 September 2004. The sample. For the determination of the total N content
total fresh weight of harvested corn with cobs was (Kjeldahl), the samples, oven-dried at 105°C, were
measured in each ridge at 3 months after seed sowing. decomposed in heated sulfuric acid and then distilled
At harvest, roots were collected from four samples of ammonia was collected. All the analyses were carried
core topsoil (5 cm in diameter and 10 cm in depth) col- out at the Soil Research Institute, Bogor, Indonesia.
lected around the center of each ridge. The root samples
in each ridge were gathered to determine the dry weight Statistical analysis
and colonization rate of AM fungi. The colonization For the results on crop yield, root dry weight and
rate of the AM fungi was determined for the randomly colonization rate of AM fungi, one-way anovas were
collected fine roots using the grid-line intercept method carried out to evaluate the difference between the
(Giovannetti and Mosse 1980) after staining with a treatments.
0.05% Trypan blue solution.
Figure 2 Effects of the application of chemical fertilizer 15-15-15 at 50 g m−2 (NPK) and bark charcoal at 10 L m−2 (Char) on the
fresh weight (FW) of harvested maize, root dry weight and the colonization rate of arbuscular mycorrhizal (AM) fungi in maize.
Control (Con): no application. Values are means ± standard error (n = 3). Columns with the same letter (a, b and c) are not
significantly different (P < 0.05).
Exchangeable
Available Bulk
Exchangeable cations acidity (cmolc kg−1)
pH pH Total C Total N P2O 5 CEO density
(H2O) (KCl) (kg kg−1) (g kg−1) (mg kg−1) (cmolc kg−1) Ca2+ Mg2+ K+ Na+ Al3+ H+ (g cm−3)
7.4 7.1 0.398 10.4 63.1 37.14 48.82 2.78 4.03 1.85 0.01 0.08 0.37
and fertilizer (Char-NPK) than after the application of The applied bark charcoal displayed a neutral pH,
fertilizer only (NPK) at Site A. Particularly for maize, an high carbon content, high CEC and high content of
approximate twofold increase in yield was obtained by exchangeable cations, particularly Ca2+ (Table 1). The
bark charcoal application. At Site B, the average yield amount of Ca 2+ was higher than the CEC, which
of cowpea and peanut in the different treatments indicates that free Ca2+ was included in bark charcoal.
showed the same tendency as that at Site A, namely, Glaser et al. (2000) suggested that the high CEC of
Con < NPK < Char-NPK, although no significant charcoal resulted from slow oxidation on the edges
difference (P < 0.05) was observed. The yield of maize at of the aromatic backbone of charcoal for the formation of
Site C is shown in Fig. 2. The yield increased significantly carboxylic groups. Based on the contents of total N and
after Char-NPK application. It was observed that the available P in charcoal (Table 1), charcoal application,
standard errors for the means of yield among the repli- 10 L m−2, was equivalent to a total N dose of 38.5 g m−2
cates were smaller in the Char-NPK application than in and an available P dose of 0.23 g m−2, respectively. A
the application of other materials. This suggests that the large amount of total N, approximately fivefold as high
yield after Char-NPK application was more stable than as that applied using chemical fertilizer, was supplied
that after a single application of NPK or Char. As the by charcoal application.
amount of applied chemical fertilizer, 50 g m−2, which The results of the soil analysis are shown in Table 2.
was equivalent to 75 kg ha−1 of each component, was Before the experiments, the amounts of available P2O5
approximately half of that of the standard fertilizer (Bray 1) and exchangeable cations and base saturation
application in the region, it was expected that the were higher at Site B than at Sites A or C. The previous
amount of fertilizer applied could be reduced by the chicken farming activities probably influenced the fer-
application of bark charcoal. tility of the soil at Site B. Soil analysis at harvest revealed
Exchangeable Exchangeable
Available Base
cations (cmolc kg−1) acidity (cmolc kg−1)
Site and pH pH Total N P2O 5 CEC saturation
Treatments (H2O) (KCl) (g kg−1) (mg kg−1) (cmolc kg−1) Ca2+ Mg2+ K+ Na+ (%) Al3+ H+
Site A
Before experiment 3.9 3.9 1.7 47.8 10.12 1.21 0.30 0.15 0.25 18.9 2.67 0.26
At harvest
Maize
Con 4.0 3.8 1.7 22.0 9.87 0.80 0.20 0.12 0.22 13.6 2.93 0.20
NPK 4.0 3.8 1.9 44.5 10.23 0.79 0.18 0.12 0.07 11.3 2.97 0.22
Char-NPK 5.1 4.5 2.4 80.2 12.72 6.21 0.45 0.25 0.13 55.3 0.12 0.12
Cowpea
Con 4.2 3.9 1.2 25.4 10.81 1.30 0.24 0.08 0.08 15.7 2.49 0.15
NPK 4.1 3.9 1.8 44.0 10.66 1.01 0.28 0.12 0.02 13.4 2.81 0.15
Char-NPK 5.3 4.8 1.6 91.8 16.42 7.80 0.43 0.29 0.14 52.7 0.02 0.12
Peanut
Con 4.2 3.9 1.9 55.3 10.21 1.27 0.29 0.08 0.07 16.7 2.41 0.15
NPK 4.0 3.9 1.8 137.5 10.01 0.91 0.22 0.10 0.03 12.6 2.77 0.20
Char-NPK 5.1 4.6 2.5 176.0 12.66 5.98 0.37 0.18 0.07 52.1 0.15 0.10
Site B
Before experiment 4.7 4.1 2.0 210.1 11.77 4.05 1.04 0.40 0.25 48.8 0.48 0.20
At harvest
Maize
Con 4.4 3.9 1.7 23.4 11.64 2.97 0.81 0.22 0.09 35.1 1.64 0.18
NPK 4.4 3.9 2.1 113.2 12.76 3.11 0.73 0.22 0.13 32.8 1.44 0.19
Char-NPK 5.6 5.1 2.4 126.6 15.42 9.32 0.82 0.31 0.13 68.6 0.00 0.02
Cowpea
Con 5.2 4.6 1.9 75.3 11.93 3.77 1.35 0.41 0.13 47.4 0.04 0.11
NPK 4.6 4.1 1.8 151.2 11.23 5.22 1.48 0.22 0.13 62.8 0.44 0.09
Char-NPK 5.8 5.3 2.4 188.2 15.11 9.30 1.10 0.53 0.13 73.2 0.00 0.02
Peanut
Con 4.6 4.1 2.0 302.9 12.31 4.56 1.39 0.59 0.13 54.2 0.26 0.15
NPK 4.5 4.0 2.0 298.7 13.21 4.51 1.19 0.53 0.10 47.9 0.40 0.16
Char-NPK 5.5 5.0 2.8 355.6 17.18 9.73 1.25 0.65 0.20 68.9 0.00 0.05
Site C
Before experiment 4.1 3.9 1.4 94.2 8.54 0.64 0.21 0.07 0.06 11.5 2.35 0.35
At harvest
Maize
Con 4.5 3.9 1.3 108.1 8.85 0.79 0.27 0.07 0.06 13.4 2.31 0.31
NPK 4.4 3.8 1.3 144.5 8.60 0.79 0.25 0.14 0.05 14.3 2.10 0.33
Char 5.4 4.5 2.1 84.3 12.38 5.86 0.55 0.21 0.09 54.2 0.11 0.21
Char-NPK 5.3 4.4 2.1 148.7 13.04 6.06 0.45 0.18 0.06 51.8 0.23 0.17
that the pH, contents of total N and available P2O5, by Tryon (1948). In contrast, the amount of exchange-
CEC, contents of exchangeable cations and base satura- able Al3+ markedly decreased after the application of
tion were generally higher after the application of bark bark charcoal. Low pH, low base saturation, high Al3+
charcoal and fertilizer (Char-NPK) than after the application content and low fertility, which are typical characteris-
of fertilizer only (NPK). The high level of available P2O5 tics of soils in the tropical region, lead to a low produc-
after Char-NPK application indicated that the application tivity of crops in this region. Therefore, amelioration of
of bark charcoal led to a high retention of nutrients. The the soil properties by bark charcoal application could
increase in base saturation as well as CEC showed that be effective in increasing crop yield particularly in the
a large amount of exchangeable cations was introduced tropical region. The effect of bark charcoal application on
by bark charcoal application. These effects of charcoal crop yield was not significant at Site B, which indicates
application on soil chemical properties were also reported that the effect would not be appreciable on fertile soils.
Saito M 1990: Charcoal as a micro-habitat for VA mycorrhizal Uddin SMM, Murayama S, Ishimine Y, Tsuzuki E 1994:
fungi, and its practical implication. Agric. Ecosyst. Envi- Studies on sugarcane cultivation. 1. Effect of the mix-
ron., 29, 341– 344. ture of charcoal with pyroligneous acid on cane and
Schmidt MWI, Skjemstad JO, Gehrt E, Kögel-Knabner I 1999: sugar yield of spring and ratoon crops of sugarcane
Charred organic carbon in German chernozemic soils. (Saccharum officinarum L.). Jpn. J. Trop. Agr., 38, 281–
Euro. J. Soil Sci., 50, 351– 365. 285.
Shindo H 1991: Elementary composition, humus composition, Uddin SMM, Murayama S, Ishimine Y, Tsuzuki E, Harada J
and decomposition in soil of charred grassland plants. 1995: Studies on sugar cane cultivation II. Effect of the
Soil Sci. Plant Nutr., 37, 651– 657. mixture of charcoal with pyroligneous acid on dry matter
Tryon EH 1948: Effect of charcoal on certain physical, chemi- production and root growth of summer planted sugar-
cal, and biological properties of forest soils. Ecol. Monogr., cane (Saccharum officinarum L.) Jpn. J. Crop Sci., 64,
18, 81–115. 747 – 753.
Summary
This research evaluated preplant in-row application of CSA on crop yield of Irish potato, sweet
corn, tomato and bell pepper at the Kentland Agricultural Research Farm, located near
Blacksburg, VA. Overall, our data are encouraging, indicating that beneficial microorganisms
(microbes) in CSA granules improved productivity of sweet corn (2006 and 2007) and tomato
(2007). Based on limited data and observations, enhanced mineralization in the rhizosphere of
CSA-treated sweet corn and tomato plants is at least partially responsible for increased uptake of
nitrogen and improved crop yield. Apparently, placement in near proximity to sweet corn and
tomato seed stimulated rapid rhizosphere development of microbial biomass and improved
effectiveness of CSA. Crop yield of Irish potato and bell pepper was not affected by CSA. Distant
placement of CSA (3-4 inches above the seed pieces in 2007) possibly accounted for lack of crop
yield response with Irish potato. Reasons for lack of yield response of CSA to bell pepper are not
know, since tomato and pepper transplants were treated the same throughout these experiments.
Description of field soil and treatments. In 2006 and 2007, all field plots were grown in an
organic transition high-quality silt loam soil having a pH of 6.4, with medium to high levels of
phosphorus, potassium, calcium and magnesium.
Irish potato and sweet corn. The research field plots both years were divided into four
replications (424 ft long and 24 ft wide), consisting of four raised beds (6 ft center to center, and
6 inches high). The top of each bed was approximately 42 inches wide, and the alleyways
between beds (bed shoulders and bottoms) were 30 inches. In September preceding each year,
two beds in each replication were seeded with forage radish (Raphanus sativus) and two beds to
crimson clover (Trifolium incarnatum). Alleyways in all plots were seeded with cereal rye
(Secale cereale). Forage radish was frost killed at approximately 20 F and crimson clover and
rye over-wintered. In mid April, bed tops were flail mowed and the residues were shallow
incorporated (2-3 inches deep) with a rototiller (Table 1).
Biomass produced (and thus mineralizable nitrogen, N) of both cover crops was considerably
less in 2006/2007 than 2005/2006. Although actual amounts of cover crop biomass and
mineralizable N were not measured, the estimated quantity of plant-available N would be
approximately 30 and 15 lb N/acre in 2006, compared to 10 and 5 lb N/acre in 2007, from
crimson clover and forage radish, respectively. Because nitrogen availability was a major
limiting factor both years, especially in 2007, these relatively small amounts of plant-available N
would have contributed relatively little to improved crop yield. In mid April of 2006 (but not in
2007), before seeding Irish potato or sweet corn, all beds were fertilized using 800 lb/acre of
Renaissance 8N-1P-5K organic fertilizer (composed of feather meal, bone meal, soybean and
potassium sulfate). The organic fertilizer was precision placed in-row and incorporated to a depth
of 5-6 inches deep in grow zones located 20-inches apart on top of the raised beds. Grow zones
are the designated row areas on raised beds where vegetables were seeded.
Growing Irish potato. Whole seed potatoes (Chieftain in 2006 and Kueka Gold in 2007) were cut
into 2-oz seed pieces, treated with Oxidate for 5 minutes, stored for 1-2 weeks and planted by
hand in 2006 and using a potato seeder in 2007 (Table 1). Seed pieces were set 10-12 inches
apart and 5-6 inches deep in the two grow zones on each bed (212 ft long). In 2006, CSA
granules (30 lb/acre) were applied before planting the seed pieces. CSA granules were hand
applied to subplots (two beds, 76 ft long) in the grow zones and incorporated to a depth of 3-5
inches with a wheel hoe. In 2007, CSA granules (20 lb/acre) were applied (after planting potato
seed pieces with the seed planter) in the grow zones and shallow incorporated (only 1-2 inches
deep) with a hand hoe. Each year, the remaining row area (136 ft long) of each row was left
untreated, of which the middle 60 ft was designated as a buffer zone separating the CSA-treated
(+CSA, 76 ft) from the untreated (no CSA, 76 ft). Plots were irrigated and hand weeded as
needed throughout the growing season. Stand counts were made and potato tubers were
harvested in late September using a two-row potato digger. In 2007, each subplot was further
divided into two equal sub-subplots (one 6-ft bed, 76 ft long, received 2 gallon of fish
concentrate/acre and a second adjacent bed received no fish concentrate—i.e., control). Each
sub-subplot was further divided into two equal sub-sub-subplots (one bed, 38 ft long) (one-half
of each sub-subplot received 80 lb N/acre as a sidedress fertilizer and the other half received no
sidedress fertilizer—i.e., control).
Growing sweet corn. Sweet corn seed (Spring Treat in 2006 and Sugar Queen in 2007) was hand
planted with and Earthway Seeder in the two grow zones (212 ft long and 20 inches apart) of the
raised beds. Immediately before seeding in both years, CSA granules were applied to subplot in-
row grow zones (76 ft long) of each bed. In 2006, CSA granules (20 lb/acre) were hand applied
and incorporated to 1-2 deep with a wheel hoe. In 2007, CSA granules (30 lb/acre) were hand
applied using the Earthway Seeder to a depth of 1-2 inches. The remaining area (136 ft) of each
bed was left untreated, of which the middle 60 ft was designated as a buffer zone, separating the
CSA-treated (+CSA, 76 ft) and the untreated (no CSA, 76 ft) sections. Plots were irrigated and
hand weeded as needed throughout the growing season. Stand counts were made and sweet corn
ears were harvested by hand (Table 1). In 2007, subplots were further divided into sub-subplots
and sub-sub-subplots, as described above for Irish potato.
Nitrogen sidedressing (2006). Two weeks after immergence, potato plants in untreated subplots
(no CSA) were sidedressed by hand at the rate of 60 lb N/acre (20 lb N from sodium nitrate and
40 lb N from feather meal). Plants in the CSA-treated (+CSA) were not sidedressed. Five weeks
after planting, sweet corn plants of both +CSA and no-CSA subplots were divided into three sub-
subplots (25 ft long) and were sidedressed by hand at three rates of nitrogen fertilizer (0, 50 and
100 lb N/acre, from a mixture of sodium nitrate and feather meal).
Tomato and bell pepper (2007). In two separate experiments, tomato (Mountain Fresh) and bell
pepper (Aristotle) were grown on small plastic covered plots (24 ft wide and 72 ft long). The
experimental design was a randomized split block, with four replications. Main plots were
transplant-growing mixes: McEnroe Lite (ML—an organic potting mix) and Metro Mix 360
(MM—an inorganic potting mix). Subplots were addition of CSA granules to the growing mixes
(1 cup CSA granules/5 gallons of growing mix): untreated control (no CSA) and CSA-treated
(+CSA—granules were thoroughly blended in the growing mixes). Seeds of tomato or bell
pepper were placed into 72-cell trays containing either untreated or CSA-treated ML or MM
growing mixes, and grown to maturity (about 7 weeks for tomato and 9 weeks for bell pepper).
At maturity, the tomato and bell pepper transplants were set by hand in previously established
raised beds covered with black plastic mulch. A starter solution consisting of hydrolyzed fish
concentrate (2 gallons/acre) was applied with water (200 gallon/acre) as a liquid drench around
the base of each transplant in all treatments. To avoid contamination, untreated (no CSA) and
CSA-treated subplots were separated by 150 ft.
A cereal rye/hairy vetch (R/HV) cover crop biculture was seeded in the tomato/bell pepper field
site in early October of 2006. Before laying off raised beds and applying black plastic mulch, the
R/HV cover crop was flail mowed and incorporated using a disk plow. No fertilizer was applied
at planting or during the growing season for either tomato or bell pepper; however, the
incorporated R/HV residues would have provided approximately 40-60 lb N/acre.
Effects of CSA on marketable crop yield. Marketable crop yield was highest in CSA-treated
plots for sweet corn (2006 and 2007) and tomato (2007). Application of CSA had no crop yield
effects for Irish potato and bell pepper (Table 2). Why different yield responses to CSA occurred
for tomato (17% increased fruit yield) and bell pepper (no response) is unknown, since both
crops were treated identically throughout the duration of the experiments. In-row placement of
CSA granules was distinctly different for Irish potato and sweet corn and could possibly account
for different yield responses to application of CSA. Granules of CSA were placed in close
proximity to sweet corn seed in both 2006 and 2007; however, in 2007, shallow incorporation of
CSA granules and deep placement of potato seed pieces (5-6 inches below the soil surface)
resulted in relatively reduced CSA-seed contact with potato, compared to sweet corn. In 2006,
CSA-seed contact was adequate; however, yield response to application of CSA granules was
confounded, because the untreated control (no CSA) potato plants were sidedressed with 60 lb
N/acre, while the CSA-treated plants were not sidedressed.
How (what mechanisms) CSA improves crop yield is mere speculation. Perhaps, CSA microbes
(at proper concentration, placement and timing) can improve absorption of plant-available soil
moisture, and/or improve rate of mineralization (release of plant-available N). Drip irrigation
was applied uniformly across all plots both years; hence, we have no evidence that improved
water absorption contributed to improved crop yield in CSA-treated plots. On the other hand,
enhanced mineralization could have accounted for the increase crop yields, as evidence by the
potato data for 2006. Potato tuber yield in 2006 was nearly identical in CSA-treated and untreated
(no CSA) plots, although the untreated plants received 60 lb N/acre as a fertilizer sidedressing,
while CSA-treated plants were not sidedressed. Since the soils in our experimental sites were
nitrogen deficient, these data indicate that more plant-available N was released (mineralized) in
CSA-treated than untreated plots.
Effect of growing mixes and CSA on marketable fruit yield of tomato. An interaction
occurred between potting mixes used for growing tomato transplants and application of CSA
granules. Tomato transplants grown in the inorganic Metro Mix 360 (MM) out yielded plants
grown in the organic McEnroe Lite (ML) by 6%; however, when CSA granules were added to
the potting mixes, tomato transplants grown in MM out yielded ML by 16% (Table 3).
Apparently, proliferation of beneficial microbes was uninhibited in the more “sterile” CSA-
treated MM, while microbial competition possibly reduced buildup of beneficial microbes in
CSA-treated ML. The result was a 22% tomato yield increase in CSA-treated MM (vs. untreated),
compared to only a 12% yield increase in CSA-treated ML (Table 3).
Effect of CSA on growth of tomato and bell pepper transplants. Application of CSA granules
to MM and ML potting mixes (priming) enhanced growth rate and size of both tomato and bell
pepper. Although not measured, transplant size at time of field setting was approximately 15-
25% larger. Enhancement in growth response to CSA priming appeared to be greater for tomato
than bell pepper. The potential of CSA priming to shorten the time required to produce
marketable transplants and subsequent increased marketable fruit yield merits further research.
(Refer to the 2006 report).
Effect of cover crops on marketable yield of Irish potato and sweet corn. There was no yield
response to cover crops in 2007 (data not shown). No yield response is highly predictable, since
growth of cover crops was severely curtailed because of delayed seeding, drought and poor plant
stands. Refer to the 2006 report for discussion of the cover crop effects on crop yield in 2006,
when growth of cover crops was excellent.
Effect of N sidedressing and liquid fish concentrate on marketable yield of Irish potato and
sweet corn in 2007. In accordance with the agreed-upon protocol, no preplant fertilizer was
applied in 2007. Therefore, since the soil at the research sites is relatively low in plant-available
N and little cover crop biomass was produced, these unfertilized plots showed a dramatic yield
response to N sidedressing (80 lb N/acre) for both Irish potato and sweet corn (Table 4), and
even showed a slight response to in-row application of liquid fish concentrate for Irish potato
(Table 5).
Table 3. Effect of priming growing mixes with CSA on marketable organic crop yield, 2007.
Bell Pepper
2006 2007
----- ----- 80 98
Sign. .001
50 98 80 96
Table 5. Effect of liquid fish concentrate applied in row at planting on marketable organic
crop yield of Irish potato and sweet corn, 2007.
0 80 61
2 91 66
Significance .05 ns
Cwt = hundredweight units (100 lb); ns = not statistically significant at p = .05.
Biochar, climate change and soil:
A review to guide future research
Important Disclaimer:
CSIRO advises that the information contained in this publication comprises general
statements based on scientific research. The reader is advised and needs to be aware that
such information may be incomplete or unable to be used in any specific situation. No
reliance or actions must therefore be made on that information without seeking prior expert
professional, scientific and technical advice. To the extent permitted by law, CSIRO
(including its employees and consultants) excludes all liability to any person for any
consequences, including but not limited to all losses, damages, costs, expenses and any
other compensation, arising directly or indirectly from using this publication (in part or in
whole) and any information or material contained in it.
Citation: Sohi, S1.Loez-Capel, E2., Krull, E3., Bol, R4., 2009. Biochar's roles in soil and climate
change: A review of research needs. CSIRO Land and Water Science Report 05/09, 64 pp..
1
Centre for Bioenergy and Climate Change, Rothamsted Research, Harpenden, AL5 2JQ, UK; now at
UK Biochar Research Centre, School of Geosciences, University of Edinburgh, UK, Email:
saran.sohi@ed.ac.uk
2
School of Civil Engineering and Geosciences, University of Newcastle, Newcastle uponTyne, NE1 7RU,
UK, Email: elisa.lopez-capel@ncl.ac.uk
3
CSIRO Land and Water, PMB2, Glen Osmond SA 5064, Australia, Email: evelyn.krull@csiro.au
4
Biogeochemistry of Soils and Water group, North Wyke Research, UK, Okehampton, EX20 2SB, UK,
Email: roland.bol@bbsrc.ac.uk
Cover Photographs:
Cover photo 1 Fragments of biochar 0.2-0.5mm diameter comprising willow stems carbonised at 600
C. Source: Saran Sohi
Cover photo 2 Scanning electron micrograph of biochar formed from rubber tree stems at
800 C in a 200kW gasification plant in rural Cambodia. Source: Simon Shackley and Erik
Middelink
© 2008 CSIRO
ACKNOWLEDGEMENTS
The preparation of this report was funded by the CSIRO Land and Water Opportunity
Development Fund.
Rothamsted Research and North Wyke Research received grant-aided support from the
Biotechnology and Biological Sciences Research Council (BBSRC) in the UK. Rothamsted
Research is an Institute of the UK Biotechnology and Biological Sciences Research Council.
Newcastle University receives grant-aided support from the Engineering and Physical
Sciences Research Council (EPSRC) in the UK.
Keith Goulding (Manager of the Cross-Institute Programme for Sustainable Soil Function
Department of Soil Science, Rothamsted Research), Peter Hairsine (Leader, Science
Development CSIRO Land and Water) and Mike Grundy (Theme Leader, Managing
Australia’s Soil & Landscape Assets. CSIRO Land and Water) provided helpful reviews and
comments that improved the final version of the report.
iii
EXECUTIVE SUMMARY
Biochar is the charred by-product of biomass pyrolysis, the heating of plant-derived material
in the absence of oxygen in order to capture combustible gases. The objective of this report
was to review and evaluate published studies with regard to what evidence and arguments
currently exist that assess the application of biochar to soil to a) sequester carbon and b)
produce secondary agronomic benefits. Current analyses suggest that there is global
potential for annual sequestration of atmospheric CO2 at the billion-tonne scale (109 t yr-1)
within 30 years. So far, however, the underlying published evidence arises mainly from
small-scale studies that do not currently support generalisation to all locations and all types
of biochar.
From the available published and peer-reviewed literature the following general findings can
be made for eight key questions. It is noted that for each of these key questions there
remains major research questions that require the attention of researchers. This summary
provides these outstanding research issues along side the major findings.
iv
low emissions technologies, the availability of alternative carbon sequestration
technologies and global policy responses to climate change. The growing price of waste
disposal is likely to make the production and application of biochar for electricity and
waste management economically viable. Carbon offsets will have a greater role once
biochar is certified under the Clean Development Mechanism (CDM) of the Kyoto
Protocol. Uncertainty over market interventions may risk the investment in energy
facilities that are able to produce biochar.
6. What are the environmental and societal benefits?
Models exist for viable agronomic use of biochar (without energy capture) in subsistence
agriculture. However, relevant technological innovation is required to deal with
environmental issues such as smoke production from traditional char production and
associated health risks. Socio-economic constraints are not adequately researched.
Higher crop yields resulting from biochar applications would be expected to mitigate
pressures on land and would also have relevance to land restoration and remediation.
Other environmental benefits of biochar application may lie in its application to
rehabilitate contaminated wetlands and as a means to assist in managing (avoiding)
algal blooms in aquatic ecosystems through adsorption of nutrients.
Biochar performance
Currently, the predictive capacity for biochar ‘performance’ does not exist and how to
best optimise the multiple useful characteristics as a function of feedstock has not been
assessed. This is currently inhibiting the realisation and application of this technology.
v
Water holding capacity and aggregate stability
While some studies report positive effects of biochar application on water-holding
capacity, the specific mechanism that biochar exerts on water retention, macro-
aggregation and soil stability are poorly understood – yet should be of critical importance
in climate change adaptation, where mitigating drought, nutrient loss and erosion are
critical.
vi
CONTENTS
1. Introduction ......................................................................................................... 1
2. Biochar ................................................................................................................. 2
2.1. What is biochar? ....................................................................................................... 2
2.1.1. Why and how is biochar made?.............................................................................3
2.1.2. Biochar feedstocks ................................................................................................5
2.1.3. Biochar production systems ..................................................................................6
2.1.3.1. Slow pyrolysis........................................................................................................7
2.1.3.2. Fast pyrolysis.........................................................................................................8
2.1.3.3. Intermediate pyrolysis............................................................................................9
2.1.3.4. Carbonisation ........................................................................................................9
2.1.3.5. Gasification............................................................................................................9
2.1.3.6. Production of ammonia during pyrolysis ..............................................................10
2.2. Biogeochemical characterisation of biochar ........................................................... 10
2.2.1. The purpose of biogeochemical characterisation ................................................10
2.2.2. Physical and chemical characterisation...............................................................11
2.2.3. Quantification of biochar and char .......................................................................13
2.2.4. Background and biochar history: from terra preta to terra nova...........................14
vii
5. Research Priorities and Future Challenges .................................................... 41
5.1. Fundamental mechanisms...................................................................................... 42
5.2. Properties, qualities and environmental risk assessment....................................... 43
5.3. Carbon cycle modelling .......................................................................................... 44
5.4. Beneficiaries ........................................................................................................... 44
5.5. Commentary on likely barriers to the adoption of a large scale enterprises utilising
Biochar.................................................................................................................... 45
References .................................................................................................................. 46
TABLE OF FIGURES
TABLE OF TABLES
viii
1. INTRODUCTION
Periodic fire across Australian landscapes results in a natural process of carbon (C)
sequestration from atmosphere to soil by the conversion of biomass to charcoal. The extent
of this process has recently been quantified for Australia (Lehmann, 2009). There are
increasing calls to mirror and enhance this process by the concerted use of ‘biochar’, a form
of charcoal produced with the simultaneous production and capture of bio-energy which is
then applied to the soil. A measure of the need and interest for a concerted effort in this area
has been the evolution of an organised consortium, known as the International Biochar
Initiative (IBI) (<www.biochar-international.org>).
The inspiration for the supplementation of soil with charcoal stems from observations made
in the ancient agricultural management practices that created terra preta, deep black soils.
These soils, found throughout the Brazilian Amazon, are characterised by high levels of soil
fertility compared with soils where no organic C addition occurred (Harder, 2006; Marris,
2006; Lehmann, 2007a; Renner, 2007). The evident value of the terra preta led to the
suggestion that investment into biochar and application to agricultural soil may be both
economically viable and beneficial. Rising fossil fuel prices, the need to raise yields in light of
the global food crisis, and the emergence of a significant global market for trading carbon
appear to promise added economic incentives in the future.
At the same time the need to protect soils under an increasingly uncertain climate makes the
apparent ability of biochar to increase the capacity for soil to absorb and store water vitally
important. It also appears that adding biochar to soil may be one of the only ways by which
the fundamental capacity of soils to store and sequester organic matter could be increased.
There are a number of detailed reviews describing charcoal formation (Knicker, 2007) and
associated C dynamics (Preston et al., 2006; Czimczik et al., 2007), including its role in the
global carbon cycle (Schmidt et al., 2000). Forthcoming is a compendium of review articles
(“Biochar for Environmental Management: Science and Technology”), which will place
existing studies in the context of pyrolysis bioenergy (Lehmann and Joseph, 2009b ).
A number of studies have now highlighted the net benefit of using biochar in terms of
mitigating global warming and as an active strategy to manage soil health and productivity
(Figure 1) (Lehmann, 2007a; Lehmann, 2007b; Lehman et al., 2005; Ogawa et al., 2006;
Laird, 2008; Mathews, 2008; Woolf, 2008). However, relatively few studies exist that make a
quantitative assessment of biochar-based soil management scenarios with regard to
greenhouse gas, energy, and economic perspectives (Fowles, 2007; Gaunt et al., 2008).
Nonetheless, the concept and value of biochar production and application is gradually
incorporated by policy makers and governments (Winsley, 2007).
Current studies are in many cases conceptually or geographically limited, and are often
constrained by limited experimental data. In particular, mechanistic descriptions of the
characteristics of biochar and its function in the soil and experimentation relevant to wide-
scale applications of biochar are currently limited. In this report we examine existing
published research within a framework constrained by a policy context. Thereby, we aim to
identify gaps where new research should be focused in a way that will enable biochar to
engage with climate change mitigation and to maintain soil productivity.
1
Fossil fuel Bioenergy Bioenergy with
biochar to soil
2. BIOCHAR
2
• Char: the solid product arising from thermal decomposition of any natural or synthetic
organic material. Examples are char from forest fire and soot resulting from the
incomplete combustion of fossil hydrocarbon.
• Charcoal: produced from the thermal decomposition of wood and related organic
materials, mainly for use as an urban fuel for heating and cooking, but also traditional
uses as soil amendment or control of odour (Okimori et al., 2003). Temperatures in
traditional kilns approach 450-500°C, which is similar to that of industrial pyrolysis but
with lower yields: conversion of feedstock dry mass may be as low as 10 % compared to
35% using more formal production technology. Also, all heat as well as gaseous and
liquid co-products are lost during the combustion process.
• Activated carbon: manufactured by heating carbonaceous material at a high temperature
(above 500°C) and over long (>10 hours) periods of time. The resulting material is
characterised by a very high adsorptive capacity. It is not used as a soil amendment but
has been applied for cleansing processes, such as water filtration and adsorption of gas,
liquid or solid contaminants (Tomaszewski et al., 2007).
• Black carbon: a general term that encompasses diverse and ubiquitous forms of
refractory organic matter that originate from incomplete combustion (Baldock et al.,
2002). The diversity of burning conditions results in black carbon occupying a continuum
of material. The review by Schmidt (1999) provides a thorough account of the ‘black
carbon’ continuum, its constituents and definitions.
Biochar from pyrolysis and conventional charcoal and char share key characteristics which
are related to carbon sequestration (long residence time) and soil fertility (soil conditioning
effect). This is important since there is currently a much greater amount of research for char
(Glaser et al., 2002) than for biochar. Biochar produced in association with bioenergy
generation may be more applicable in some countries than others, depending on economic
circumstance, political priorities, technology and infrastructure.
The central quality of biochar and char that makes it attractive as a soil amendment is its
highly porous structure, potentially responsible for improved water retention and increased
soil surface area. Addition of biochar to soil has also been associated with increased nutrient
use efficiency, either through nutrients contained in biochar or through physico-chemical
processes that allow better utilisation of soil-inherent or fertiliser-derived nutrients.
Importantly, it is the apparent biological and chemical stability that allows biochar to both act
as a carbon sink, as well as provide benefits to soil that are long-lived.
Using pyrolysis to turn sustainably produced biomass into a recalcitrant substance that is
decomposed at a much slower rate, constitutes both a tool for carbon sequestration and
avoided emission. It is argued that sequestration of carbon in biochar allows for a much
longer storage time compared with other terrestrial sequestration strategies, such as
afforestation (Schulze et al., 2000). The stability and carbon sequestration potential of
biochar in soil is examined in Section 3.1.2.
Modern industrial bioenergy systems involve pyrolysis and gasification, the heating of a
biomass feedstock under controlled conditions to produce combustible synthesis gas
(‘syngas’), and oil (‘bio-oil’) that can be burnt to produce heat, power, or combined heat and
power. Biochar, the third combustible product produced in pyrolysis, is the solid charred and
carbon-rich residue.
The balance in energy release and biochar formation can be optimised. Effectively, it is a
‘combustion’ process that may be curtailed at a point where any desired ratio in these
products has been achieved. This ratio can then be adjusted and re-optimised to satisfy
changing objectives. Whereas simple combustion of a feedstock maximises energy yield per
unit mass, combusting syngas from pyrolysis gives – where optimised for biochar – a much
greater energy yield per unit of carbon release.
3
If incorporating biochar into soil can reliably deliver the environmental benefits outlined in
3.1.2, the carbon-equivalent saving resulting from conversion of biomass using pyrolysis can
be increased further, relative to the production of energy only (i.e. combustion).
Globally, there is an estimated 15x109 ha of cropland (Ramankutty et al., 2008). On the basis
of calculations by Gaunt (2008), the application of biochar once every ten years to this land
area would result in a CO2 -equivalent gain of 0.65 GtC yr-1.
Pyrolysis has a requirement for initial energy, in the same way as in straight combustion
some heat in the flame is used to initiate combustion of new feedstock. But the relative
requirements must be carefully compared, together with any difference between pyrolysis
and alternative bioenergy technologies in the energy requirement of feedstock transportation
and drying.
The potential advantage of pyrolysis-derived bioenergy over other bioenergy strategies in
terms of greenhouse gas emissions results not only solely from the retention of up to 50% of
the feedstock carbon in stable biochar, but from indirect savings that may result from the use
of biochar in agriculture, specifically the soil (Gaunt et al., 2008).
Biomass pyrolysis and gasification are well established technologies for the production of
biofuels and syngas. However, commercial exploitation of biochar by-products as a soil
amendments is still in its infancy. In Japan, which has the largest market for such products,
approximately 15 000 t yr-1 is traded annually for soil use (Okimori et al., 2003). More usually
biochar products are gasified for extraction of residual energy, or used in production of high
value products such as activated carbon (Demirbas et al., 2006b).
The pyrolysis process greatly affects the qualities of biochar and its potential value to
agriculture in terms of agronomic performance or in carbon sequestration. The process and
process parameters, principally temperature and furnace residence time, are particularly
important; however, the process and process conditions also interact with feedstock type in
determining the nature of the product.
4
These variables together are key influences on the chemical, biological and physical
properties, which limit the potential use for biochar products. A summary of feedstock,
production processes and products is illustrated in Figure 2. The assignment of feedstock to
process in Figure 2 is based on examples from the literature and does not indicate that they
should be an exclusive classification.
Each category of pyrolysis process is characterised by a contrasting balance between
biochar, bio-oil and syngas (Table 1). The precise ratio in these products may vary between
plants, and may be optimised at a particular installation; however, it is critical that maximising
the production of biochar relative to mass of initial feedstock (Demirbas, 2006), is always at
the expense of usable energy in the liquid or gaseous form. Although a greenhouse gas
mitigation strategy may favour maximising the biochar product (Gaunt et al., 2008), the
balance that is realised is a function of market and engineering constraints.
In a generalised analysis, the economic cost of maximising the retention of carbon in biochar
using slow pyrolysis has been assessed against the possible net gain in CO2 –equivalent
emissions from using the product in soil, after accounting for the additional fossil-carbon
offset that could be obtained through complete combustion of the feedstock (Gaunt et al.,
2008). The net carbon gain over fossil fuel scenarios was 2–19 t CO2 ha-1 y-1, encompassing
figures 2–5 times higher than those for strategies based on biomass combustion. The eligible
portion of this added saving would have to attract CO2 -offset at a value sufficient to cover
the USD 47 t-1 value of residual energy in biochar. A more detailed description of this
analysis and discussion of the competing processes associated with energy and char
production is discussed in detail in Chapter 3.
Table 1. Fate of initial feedstock mass between products of pyrolysis processes (IEA, 2007)
FAST PYROLYSIS
75%
Moderate temperature (~500 °C) 12% 13%
(25% water)
Short hot vapour residence time (<2s)
INTERMEDIATE PYROLYSIS
50%
Low-moderate temperature, 25% 25%
(50% water)
Moderate hot vapour residence time
SLOW PYROLYSIS
30%
Low-moderate temperature, 35% 35%
(70% water)
Long residence time
GASIFICATION
5% tar
high temperature (>800 °C) 10% 85%
5% water
Long vapour residence time
Although current results suggest that the type of feedstock used for pyrolysis is more
important where biochar is to be applied as a soil conditioner (Section 3.2.) there is little
consensus as to what constitutes optimal feedstock for energy production.
This is mainly due to the fact that the number of existing commercial plants is small, and that
these plants are dedicated to specific waste streams, giving little incentive to experiment with
this parameter. However, some research-scale pyrolysis plants have conducted experiments
with a wider range of feedstocks (Day et al., 2005; Das et al., 2008; Gaunt et al., 2008).
Feedstocks currently used at a commercial-scale or in research facilities include wood chip
and wood pellets, tree bark, crop residues (including straw, nut shells and rice hulls), switch
grass, organic wastes including distillers grain, bagasse from the sugarcane industry and
5
olive waste (Yaman, 2004), chicken litter (Das et al., 2008), dairy manure, sewage sludge
(Shinogi et al., 2002) and paper sludge.
The elemental ratios of carbon, oxygen and hydrogen are key feedstock parameters in
commercial use and the quality of fuel products (Friedl et al., 2005). The feedstocks which
are favoured for bio-oil and fuel-gas are those that have low mineral and N content. These
include wood and biomass from energy crops, including short-rotation woody plants (such as
willow), high productivity grasses (such as Miscanthus spp.), and a range of other
herbaceous plants. They may also include abundant, available and low-cost agricultural by-
products, including cereal straw.
The proportions of hemi-cellulose, cellulose and lignin content determine the ratios of volatile
carbon (in bio-oil and gas) and stabilised carbon (biochar) in pyrolysis products. Feedstocks
with high lignin content produce the highest biochar yields when pyrolysed at moderate
temperatures (approx. 500 °C) (Fushimi et al., 2003; Demirbas, 2006). In the future, selection
of feedstock may be dictated by the desired balance between pyrolysis products (gas, oil and
biochar), and whether the production process is slow pyrolysis, or a related process.
Charring of agricultural waste products such as nut shells and rice hulls for energy
production may be advantageous compared to disposal as waste by some other means
(Demirbas, 2006; Demirbas et al., 2006a). Alternative use for such materials includes
composting and mulching. However, it is important to recognise that continuous removal of
crop residues from the same land compromises soil cover and diminishes soil nutrient
supply. This is further discussed in Chapter 3.
6
Figure 3. Illustrative slow pyrolysis process (Source: BEST Energies)
Char
separation
Gas
Pyrolysis
Fluid bed
Drying Grinding CFB Bio-oil
Biomass to < 10% water to < 3mm Transported bed
Rotating cone cool and
Entrained flow collect
Ablative
Etc. Char
Figure 4. Schematic process diagram for fast pyrolysis (modified from Bridgewater (2006))
Slow pyrolysis is the thermal conversion of biomass by slow heating at low to medium
temperatures (450 to 650°C) in the absence of oxygen, with the simultaneous capture of
syngas. Feedstocks in the form of dried biomass pellets or chips of various particle sizes are
fed into a heated furnace and exposed to uniform heating, generally through the use of
internal or external heating as retort furnace or kilns, respectively. Conventional production
conditions have been summarised by Peacocke and Joseph in <http://www.biochar-
international.org/images/Terminology.doc> :
• residence times: >5 seconds for the production of syngas; minutes, hours or days for
biochar production
• relatively low reactor temperatures (450-650°C)
• reactor operating at atmospheric pressure
• very low heating rates, ranging from 0.01–2.0°C s-1
• very short thermal quenching rate for pyrolysis products: minutes to hours.
7
Several commercial facilities generate syngas and biochar using a continuous flow system in
which feedstock passes slowly through a kiln in an auger feed, with combustible syngas
continuously drawn away.
Biochar, bio-oil and syngas are formed in approximately equal proportions due to the slow
speed of the combustion process, which promotes extensive secondary reactions within
biochar particles and in the gas and vapour phases, leading to condensation.
The pyrolysis reaction itself is mildly endothermic, with the bulk of energy capture being in
the form of the syngas and bio-oil condensates. The biochar has a residual energy content of
about 30–35MJ kg-1 (Ryu, 2007), and conventionally this is extracted within the plant by
burning or gasification, providing heat to drive the primary pyrolysis (Demirbas, 2006), or to
dry incoming feedstocks. The syngas product may be combusted on site to generate heat or
electricity (via gas or steam turbine), or both.
A variant of slow pyrolysis includes a steam gasification step, a technology developed by
Eprida in collaboration with the University of Georgia (<http://www.eprida.com/hydro/>).
Adding steam to the pyrolysis reaction liberates additional syngas from the biochar product,
mainly in the form of hydrogen. The biochar that remains after this ‘secondary’ pyrolysis
displays rather different properties from the primary product, differing in pore size and carbon
to oxygen ratio (Demirbas, 2004).
Syngas can be purified through a sequence of operations to yield pure streams of the
constituent gases: hydrogen (50% of gas yield), carbon dioxide (30%), nitrogen (15%),
methane (5%), and lower molecular weight hydrocarbons, as well as some carbon monoxide
(Day et al., 2005). There is a small energy penalty associated with these steps.
Slow pyrolysis research plants currently process feedstock at a rate of 28–300 kg hr-1 on a
dry mass basis, and commercial plants operate at 48–96 t d-1. Comparing the efficiency of
pyrolysis plants is complex since the mix and use of products vary, and the composition and
heat value of syngas differs. Feedstock quality and moisture content is also variable, and
there is a conversion loss in the generation of electrical power through steam or gas turbines.
Very rapid feedstock heating leads to a much greater proportion of bio-oil and less biochar
(Table 1). It was with the objective of achieving this high yield of liquid fuel that fast pyrolysis
technology was developed.
The time taken to reach peak temperature of the endothermic process (the ‘resistance time’)
is approximately one or two seconds, rather than minutes or hours as is the case with slow
pyrolysis. The lower operating temperature also enhances the overall conversion efficiency
of the process relative to slow pyrolysis.
Maintaining a low feedstock moisture content of around 10% and using a fine particle size of
<2mm permits rapid transference of energy despite relatively moderate peak temperatures of
around 450°C (and in the range 350 to 500°C). In many systems the transfer is further
increased by mechanically enhancing feedstock contact with the heat source or maximising
heat source surface area. Various technologies have been used and proposed or tested
including: fixed beds, augers, ablative methods, rotating cones, fluidized beds and circulating
fluidized beds. Surface charring must be continuously removed during reaction to prevent
pyrolysis of particle interiors being inhibited by its insulating effect.
Bio-oil is condensed from the syngas stream under rapid cooling, with the combustion of
syngas providing the pyrolysis process heat. The bio-oil is a low grade product with a calorific
value, on a volume basis, approximately 55% that of regular diesel fuel. It is unsuitable as a
mainstream liquid transport fuel even after refining, and is most suitable as a fuel-oil
substitute. It is considered to have an advantage over typical fuel oils in zero SOx and low
NOx emission on combustion (Bridgewater, 2004). In addition to combustion for electricity
generation, bio-oil may be converted to syngas for production of clean fuels (gasification).
8
Bio-oil also contains high value bio-chemicals of relevance to food and pharmaceutical
industries.
The biochar product of fast pyrolysis is granular and displays a lower calorific value (23–
32 MJ kg-1) than that of slow pyrolysis (Demirbas, 2001). However, there are currently no
published studies to assess the effects of biochar from fast pyrolysis when it is applied to
soil. It is highly likely that condensed volatiles will be present in the product and that this will
affect its performance and desirability.
This term describes a hybrid technology under evaluation at Aston University, UK, designed
to produce bio-oil with very low tar content, with perceived potential for use as a motor fuel.
The process has been tested with woody and non-woody feedstocks, and produces biochar
in greater quantity and of contrasting quality as compared to fast pyrolysis.
2.1.3.4. Carbonisation
2.1.3.5. Gasification
Gasification is the process by which any carbonaceous material (coal and petroleum as well
as biomass) is substantially converted into a stream of carbon monoxide and hydrogen in a
high temperature reaction and controlled-oxygen environment, sometimes at high pressures
of 15–50 bars (Bridgewater, 2006). The gas mixture is the key energy output and the
gasification process has an application as a clean waste disposal technique (Bapat et al.,
1998). In slow pyrolysis facilities, gasification is often used to generate further syngas from
biochar ‘waste’.
Syngas may be used for electricity generation via gas or steam turbines (or both), used to
manufacture chemicals and fertilisers, or further cleaned for use as liquid fuel. Since
conversion of feedstock to syngas is often the main objective, the process is maximised for
gas production and so the biochar yield from gasification tends to be very low (Table 1).
However, this also carries the risk of higher levels of metals and minerals that may be
9
concentrated in biochar, with potential safety implications with regard to application to soil
(Fernandes et al., 2003a). Although biochar from gasification has a high calorific value
(Demirbas, 2006; Demirbas et al., 2006a), it has high value use as the basis for activated
carbon production. Its potential to act as the carrier in a slow nutrient release fertiliser
product has also been noted (Ueno, 2007).
Worldwide, gasification has been used on a commercial scale worldwide for more than 50
years, mainly in the refining, fertiliser, and chemical industries, and for more than 35 years in
the electric power industry. There are more than 140 gasification plants currently in
operation, with worldwide gasification capacity projected to grow 70% by 2015, with 80% of
this growth occurring in Asia (Anon, 2008). The majority of gasification plants produce
chemicals, mainly methanol or ammonia and urea, and use coal or refuse-derived feedstocks
(Kedco, 2008). However, biomass feedstocks are also used, for example wood pellets, wood
chips or paper and sugar cane bagasse (Ueno et al., 2007), and rural gasification projects
are expanding.
In the Haber-Bosch process, a fossil hydrogen source (usually methane) is used to fix
atmospheric nitrogen and create ammonia for manufacture of fertiliser. Hydrogen in syngas
streams from pyrolysis (7-8% of slow pyrolysis syngas) can substitute methane and be used,
potentially not only to create ammonia but, if conducted on the same site as the pyrolysis, fix
ammonia to a biochar co-product. This offers the prospect of a crop fertiliser that
simultaneously adds stabilised carbon to soil, possibly with slow release characteristics. This
could offer greater net benefit in terms of CO2 -equivalents than using syngas to, for
example, generate electricity. The process of fixing ammonia from the hydrogen syngas
stream at atmospheric pressure and ambient temperature has been demonstrated (Day et
al., 2005) and is illustrated diagrammatically in Figure 5. However, agronomic evaluation of
the product has not been published and the concept has not yet been commercialised.
Figure 5. Simplified flow chart of how biomass releases energy as it captures CO2 as
ammonium carbonate (modified from Day et al., 2005 )
Although commercial biochar products are being developed for use in soil, credit for carbon
storage will require predictable levels of stability and the ability to verify actual rates of
degradation through quantitative soil analysis (Ogawa et al., 2006; Matthews, 2008).
Identifying the characteristics that determine the stability of biochar will enable its properties
to be optimised and standardised in production. Techniques to unambiguously detect and
10
measure its abundance in soil are necessary to verify its application and to trace the fate of
particular biochar products.
Biogeochemical characterisation techniques may also help understand the function of
biochar products in soil at the process level. With specific knowledge of the nature of
biochar-driven processes in the soil, predictive capacity for the longevity and reactions of
biochar in soil that will determine its value as a soil carbon sink and soil conditioner are
possible.
From a practical point of view it is important that the methods devised enable biochar
characteristics to be determined sufficiently rapidly and inexpensively to permit widespread
application and use.
Kuwagaki (1990) proposed that seven properties should be measured for a quality
assessment for agronomically-used biochar: pH, volatile compound content, ash content,
water holding capacity, bulk density, pore volume, and specific surface area.
Feedstock is a primary factor governing the chemical and physical properties of biochar. The
elemental composition reported for a range of bio-oil and biochar products from various
feedstocks are compared in Table 2.
Table 2. Reported elemental composition for a range of bio-oil and biochar products (% dry
ash-free mass)
Elemental composition (%) HHV*
Product C H N O (MJ/kg)
*HHV= higher heating value (enthalpy of complete combustion of a fuel including the
condensation enthalpy of former water); Demirbas et al.,(2004)
In general, the carbon content of biochar is inversely related to biochar yield. Increasing
pyrolysis temperature from 300 to 800°C decreased the yield of biochar from 67 to 26% and
increased the carbon content from 56 to 93% (Tanaka, 1963). Beyond a certain threshold,
the mass of biochar may decrease without any affect on the amount of carbon retained within
it; but as mass is lost, the ash content of biochar increases. In one study, the proportion of
biochar comprised of ash increased from 0.67 to 1.26% between 300°C and 800°C
(Kuwagaki and Tamura, 1990).
For a particular feedstock, the elemental composition of the pyrolysis products can still be
greatly affected by the processing temperature and pyrolysis residence time. The effect of
temperature on the composition of biochar from sugarcane bagasse is listed in Table 3.
11
There was a corresponding impact on the pH of the biochar from 7.6 at 310°C to 9.7 at
850°C (Kuwagaki and Tamura, 1990).
nd=not determined
There are inevitable accompanying differences in the physical and other chemical properties
of biochar. Scanning electron microscopy (SEM) is often used to describe the physical
structure of biochar, and the architecture of cellulosic plant material is clearly retained (Figure
6). It has been suggested that the porous structure of biochar can explain its impact on soil
water holding and adsorption capacity (Day et al., 2005; Ogawa et al., 2006; Yu et al., 2006).
Figure 6. Scanning electron microscope (SEM) image of biochar produced at 400°C from
pelletised peanut shell (Jason Nadler, Eprida, Day et al., 2005)
12
Process temperature greatly affects the surface area of pyrolysis products. In one study,
surface area was shown to increase from 120 m2g-1 at 400°C to 460 m2g-1 at 900°C (Day et
al., 2005). This effect of temperature has led to suggestions that biochar created at low
temperature may be suitable for controlling the release of fertiliser nutrients (Day et al.,
2005), whilst high temperature biochars would be more suitable for use as activated carbon
(Ogawa et al., 2006). The surfaces of low temperature biochar are, however, hydrophobic
and this may limit the capacity to store water in soil.
The form and size of the feedstock and pyrolysis product may affect the quality and potential
uses for the biochar product. Initially, the ratio of exposed to total-surface-area of biochar is
affected by its particle size. However, although low temperature biochar is stronger than high
temperature products, it is brittle and prone to abrade into fine fractions once incorporated.
Thus, over the long term, surface area, i.e. of weathered biochar, may not be greatly affected
by this parameter.
Biochar comprises part of a continuum of materials described as ‘black carbon’ (Schmidt et
al., 2001), which are difficult to quantify. Techniques that have been used to characterise this
wider class of materials – which includes soot, charcoal, and char from vegetation fire – may
be applied to detect the presence of biochar in soil, sediments and air.
These methods include extractive techniques analogous to those applied to soil organic
matter, solid state 13C nuclear magnetic resonance (NMR) spectroscopy (with cross-
polarization, CP, or Bloch decay, combined with magic angle spinning, MAS), diffuse
reflectance infrared Fourier transform spectroscopy (DRIFT), and near-edge X-ray
absorption fine structure (NEXAFS) spectroscopy (Baldock et al., 2002; Fernandes et al.,
2003b; Lehmann et al., 2005b).
Biochar occurs naturally in soil as a consequence of wildfire (see Section 3.1.5.1.) and is
considered to be a distinct soil carbon pool (Krull et al., 2003). Research to quantify and
characterise this material has highlighted the limitations of various analytical techniques
when applied to soil and separation procedures to physically separate char from other soil
organic matter. A key problem is the interference that the mineral matrix poses, particularly
with its associations with highly stabilised soil organic matter, which chemically resembles
char. This has been successfully addressed through the use of high energy ultraviolet photo-
oxidation, which oxidises most non-char carbon (Smernik and Oades, 2000; Smernik et al.,
2000). Thermal oxidation to remove lignin (De la Rosa et al., 2008) and chemical oxidation
using hydrofluoric acid to remove mineral interferences (Simpson and Hatcher, 2004a) have
also been used.
13
al., 1999; Smernik et al., 2002), thermal analysis (De la Rosa et al., 2008; Hammes et al.,
2007) and hydrogen pyrolysis (Ascough et al., 2008).
Mid-infrared spectroscopy shows promise as a means to rapidly estimate black carbon (Janik
et al., 2007) and has been applied to large sample sets (Lehmann et al., 2008). This is a
correlative technique calibrated against a reference method.
S lig h tly
c h a rre d Char C h a rc o a l Soot GBC
b io m a s s
m m a n d la rg e r m m to s u b m ic ro n
p a rtic le s s u b m ic ro n
h ig h ly in e rt
re a c tiv e
U V O X ID A T IO N – 13C NM R
u ltra -h ig h re s o lu tio n
m a s s s p e c tro m e try
th e rm o -c h e m ic a l
v is u a l / m e th o d s
m ic ro s c o p ic
c h e m ic al
m e th o d s
BCPAs
o th e r m o le c u la r
m a rk e rs
2.2.4. Background and biochar history: from terra preta to terra nova
The terra preta of the Brazilian Amazon are anthropogenic dark earths, characterised by
enhanced levels of soil fertility and popular locally for growing cash crops such as papaya
and mango. These crops are said to grow three times faster than on surrounding land, a
landscape characterised by soils of generally low fertility. Although the terra preta occur in
small patches averaging 20 ha, sites as large as 350 ha have been reported (Smith, 1999).
Similar soils have not only been identified elsewhere within the region, namely Ecuador and
Peru, but also beyond, in West Africa (Benin, Liberia), and the savanna of South Africa
(Lehmann et al., 2003).
The terra preta display high levels of soil organic matter (SOM) and nutrients such as
nitrogen, phosphorus, potassium and calcium (Table 4). These characteristics and their high
fertility is attributed in part to a high char content (Glaser et al., 2001), which is the main
reason why the terra preta tend to be much darker in colour than adjacent soils (Figure 8).
The source of the large amounts of char is considered to have been incompletely combusted
biomass carbon, such as wood from kitchen fires or in-field burning, conducted by relatively
large and settled communities in the distant past.
14
The terra preta phenomenon has widespread public appeal and has attracted extensive
coverage in popular science publications, TV and film, and a plethora of websites. The
potential relevance of the terra preta as a model for modern day variants using by-products
of bioenergy is now well established and recognised in popular science (Lehmann, 2007b;
Baskin, 2006) as well as high impact scientific journals (Marris, 2006; Lehmann, 2007a).
From this, the idea of terra nova has emerged: soils whose properties would be enhanced by
modern variants of the management practices that created terra preta,
Figure 8. Comparison of profiles of terra preta and adjacent soils (Source: IBI website)
Table 4. Physico-chemical properties of terra preta and adjacent soils (data from Solomon et
al., 2007; Liang et al., 2006)
Total
Organic soil
Depth Clay carbon nitrogen
range content (mg g-1 (mg g-1 C:N
Site Soil type (cm) Age (yr) (% soil) pH soil) soil) ratio
15
3. BIOCHAR APPLICATION IN AGRICULTURE
In the context of this report, carbon sequestration is the primary driver for considering the
application of biochar to soil. Policy makers charged with meeting greenhouse gas emission
targets and addressing public concern over increasingly evident climate change may
recognise the potential for biochar-based strategies. The land-owner or farmer is likely to
have a more practical or financial perspective.
A particular combination of feedstock, pyrolysis technology, energy conversion and by-
product usage can comprise a biochar-based system. Alternative systems have different
greenhouse gas balances. In Section 3.1.4, economically and politically conceivable systems
for different regions of the world are considered. The future price of carbon and the inclusion
of biochar in carbon-trading schemes is a key factor. The likely additional benefits of biochar
to agricultural production are reviewed in Section 3.2. These factors are critical since they
dictate whether relevant practices are adopted on a large scale through their effect on the
decision making of individual farmers.
From a global and policy perspective the potentially negative impacts of biomass use on
climate forcing must be considered. These include the effects of soot and trace gases that
are emitted into the atmosphere during combustion. Airborne transport and deposition of soot
has been implicated in the acceleration of polar ice melt, but conversely in facilitating cloud
formation and ‘global dimming’ (McConnell et al., 2007; Ramanathan et al., 2008).
Currently biomass burning accounts for 10% of global CH4 emissions and 1% of N2O
(Crutzen et al., 1990). Although current charcoal production activity could account for a
component of these emissions (Woolf, 2008), a general shift to pyrolysis-based systems
would decrease, if not eliminate, them. However, the net result with great expansion of
alternative bioenergy systems has not been assessed.
As is apparent in the terra preta, the addition of biochar can dramatically darken the colour of
soil, especially in soils that are low in organic matter. A relationship between soil colour and
low temperature fire occurrence has been demonstrated (Ketterings et al., 2000). Oguntunde
(2008) found soil at charcoal manufacturing sites to have 8% greater hue, and 20% higher
value and chroma. Since dark soils absorb more solar energy they may, depending on water
content and plant cover, display higher soil temperatures (Krull et al., 2004). This will affect
rate processes, enhancing the cycling of nutrients and potentially extending the growing
season in seasonal climates. In Japan it is a traditional farming practice to apply charcoal to
accelerate snow melt. Anecdotal evidence suggests more rapid crop establishment in
temperate soils enriched in char, but to date no quantitative relationships between biochar
application rate and these parameters have been reported. The study of Oguntunde (2008)
showed a one-third reduction in soil albedo in soils enriched in char. On a large spatial scale,
the application of biochar could affect the albedo of the Earth’s surface. Increasing surface
albedo has been proposed as a possible mitigation measure for climate forcing (Crutzen,
2006).
The frequency with which potentially toxic compounds materialise in biochar and their
concentration is inadequately researched. Two classes of compounds are of generic
concern, since they can potentially from in the pyrolysis of any feedstock: polycyclic aromatic
hydrocarbons (PAH) and dioxins. These compounds and available evidence for their
presence in biochar is examined in Section 3.2.6.
16
(Schmidt, 2004; Simpson and Hatcher, 2004b). However, the potential to enhance the
contribution that char makes to the natural carbon cycle through the addition of biochar in soil
is a topic of much public discussion and a rising profile in influential policy circles, for
example, in Australia (Garnaut, 2008). The contribution that such strategies can have on
climate change mitigation depends on attaining a much more extensive research base and
detailed economic analyses.
It is useful to consider a biochar-based strategy against more established approaches to
increase the organic carbon stored in soil, such as the use of manures and composts. The
longevity of biochar in the soil is an important element when comparing pyrolysis bioenergy
and biochar production with conventional bioenergy strategies, in mitigating climate change.
However, it is also vital to assess any indirect reduction in net greenhouse gas emissions
from agriculture through the use of biochar. There may be additional benefits arising from the
contribution of biochar to facilitating agricultural development and improving the socio-
economic circumstances of farmers in developing countries. Figure 9 captures the
complexity of potentially beneficial interactions of biochar in the context of natural cycles and
anthropogenic interventions.
In order to understand the potential significance of carbon in soil in the form of biochar, its
characteristics and dynamics should be compared to those of the remaining soil organic
matter, which accounts for most of the carbon that exists in soil (the exception being
calcareous soils which contain stocks of inorganic carbon in carbonate minerals). Depending
on land-use and climate, most soils contain up to approximately 100 t ha-1 carbon as organic
matter. Peat soils, though, comprise mainly organic matter and contain much more carbon
on a per unit area basis. It is increasingly recognised, however, that a greater proportion of
the total carbon may comprise an accumulated store of the products of burning or fire
(Skjemstad et al., 2004a), and that this has implications for the response of the wider soil
carbon pool to climate change (Skjemstad et al., 1999; Lehmann et al., 2008).
Modelling indicates that about 90% of the organic matter present in soils turns over on
decadal to centennial timescales (Coleman et al., 1996; McGill, 1996). Most organic matter in
soil is derived from plant roots, plant debris and microbially re-worked substances. The
presence of soil organic matter is important for a range of useful soil properties, which has
been comprehensively reviewed by Krull (2004). The process of microbial energy acquisition
(and concomitant CO2 release) from substrate is accompanied by a release of various
nutrient elements, which may be conserved in the soil in microbial biomass or the particulate
residues of substrate decomposition. A portion of certain nutrients may also be released in
soluble form, and a fraction may be lost from the soil through leaching or run-off; which is
essential to crop nutrition. This is particularly the case where external nutrient provision (from
fertiliser or manure) is limited or absent.
Overall, a balance slowly develops between the rate of carbon addition and the emission of
CO2, which are specific to the land-use and environmental conditions. The amount of organic
matter maintained once this balance is reached, depends on its average rate of turnover. To
date there have been few means proposed that permit manipulation of this rate, so that soil
carbon can be permanently increased. Beyond simply increasing the amount of external
organic matter inputs (Smith et al., 2000), the main strategies are to disturb the soil less by
using less intensive tillage or zero tillage (Lal, 1997; Smith et al., 1998), or by selecting
particularly recalcitrant, lignin-rich amendments (Palm et al., 2001).
Although conversion to no-till soil management has been widely promoted as an approach to
enhance soil organic matter as well as to control erosion and conserve water, the main effect
appears to be a vertical re-distribution of organic matter, and an increase toward the surface
more or less matched by a corresponding depletion at depth (Bhogal et al., 2007; Blanco-
Canqui et al., 2008). Nonetheless, the Chicago Climate Exchange includes a specification for
‘conservation tillage’ amongst its Carbon Financial Instruments for carbon sequestration and
thus a precedent for the active engagement of farming in the carbon market
17
(<http://www.chicagoclimatex.com/>). Managing decomposition in soil by manipulating the
quality of inputs has been explored extensively in tropical environments where decay is rapid
(Palm, 2001). But simply altering the composition of soil inputs has only a relatively minor
impact on the composition and long-term fate of the small portion that is stabilised, with
incorporation and repeated decomposition inside the dominant, slow turnover pool.
Thus the main emphasis in the sequestration debate has been focused on increasing soil
carbon by increasing organic matter additions in the form of straw or other crop residues, and
from external sources such as manures and a range of organic wastes: sewage sludge,
municipal compost, paper waste, and so on. Although there is a large amount of such
material available, the quantity is relatively small compared with the total flux through soil,
particularly the size of the global soil carbon pool. When a soil is at an equilibrium, only about
10% of the carbon added to soil is stabilised for more than one year. During a transition,
progress to new equilibrium is slow, with the annual increase being small relative to the
carbon invested. As equilibrium is approached the annual rate of accumulation decreases,
and once reached, the new level of input has to be sustained simply to maintain it.
Furthermore, the capacity to store organic matter is ultimately limited (with the capacity
varying with soil type, water regime and climatic factors); thus the improvement in carbon
storage that is possible for each incremental increase in input (Stewart et al., 2007; Gulde et
al., 2008). As well as added carbon being rapidly re-emitted into the atmosphere, carbon is
lost in the formation of soil organic matter through digestion in the animal gut or oxidation in
conversion to compost. The level of carbon sequestration or offset that could be realised
through an alternative use of these materials, including fossil fuel substitution, must be
considered when assessing the efficacy of these strategies from the perspective of climate
mitigation alone (Schlesinger, 2000). For example, the carbon cost of producing N fertiliser is
relevant when proposing to increase soil carbon storage indirectly through enhanced plant
growth (Schlesinger, 2000).
CO2
CROP ENERGY
productivity capture
AGRICULTURAL
development
Figure 9. The key physical (purple arrows), natural (orange arrows) and anthropogenic (red
arrows) interactions of biochar in the environment
18
In the context of the interventions generically referred to as ‘management options’, important
soil physical benefits may be gained by accumulating soil organic matter (Janzen, 2006).
However, these must be balanced against the opportunity costs, the forgone benefits that
might arise from its breakdown and turnover, most importantly the release of crop nutrients
(Janzen, 2006). In general, however, any form of organic matter added to the soil degrades
resulting relatively quickly in CO2 emission. Thus adding degradable organic matter into the
soil is inefficient in terms of climate change mitigation, with the energy contained being
captured and dissipated by soil microbes rather than in power plants where it can offset fossil
fuel use (Woolf, 2008).
Turning biologically-derived organic matter into a highly stabilised form can decrease CO2
emission from soil by considerably lowering its rate of decomposition. Whether stabilisation
by conversion to biochar represents a net carbon saving depends on the time horizon for the
comparison. However, the immediate CO2 emission from syngas released by pyrolysis
would, within a few months, be exceeded by the CO2 emitted in decomposition if the same
material had been added to soil directly (Lehmann et al., 2005a). Also, although there is a
CO2 emission associated with provision of heat for the pyrolysis process, the calculations of
Gaunt (2008) indicate that it is relatively small; in an example where pyrolysis consumed
40% of the carbon in the feedstock (in producing syngas), the CO2 resulting from provision of
process heat for that process would equate to only a further 10%. Even in temperate
environments where decomposition in soil is relatively slow, it is calculated that within two to
five years, the effective emission in the pyrolysis scenario is already less than that which
would have accrued from the soil (Gaunt et al., 2008). Over a period of the one to five
decades relevant to mitigation of climate change, the net saving is therefore considerable.
Even within the first few years, however, the higher initial loss of CO2 may be offset by the
effects of biochar on other soil processes, in particular prevention of N2O and CH4 release
from soil. Natural emissions of N2O from soil are a function of soil moisture status and
possibly tillage (Pekrun et al., 2003). Because biochar in soil may modify the moisture regime
and physical location of water within the soil matrix, it may mitigate the enhanced emission of
N2O that may occur in no-till systems. Methane emissions produced from agricultural soils,
mainly under paddy rice agriculture, account for 12% of the global methane emission from all
sources. Some studies have suggested that addition of biochar may partially suppress
methane emissions. The evidence for these effects is examined in Section 3.1.6.2.
There may be additional, potentially important offsets of other indirect emissions. These
could include avoided emission of CO2 if the fertiliser required to produce a tonne of product
is decreased via a positive effect of biochar on crop use efficiency. This extends to avoided
emissions of N2O during the manufacture of the fertiliser as well as from the soil upon
application – it is estimated that a carbon-equivalent emission of 1.8 tC is associated with
production and use of 1000 kg of fertiliser nitrogen (Mortimer, 2003). Any effect of biochar on
increased crop yield could significantly ease pressure on natural lands if implemented on a
large scale. Since the conversion of forest or savannah to agriculture can result in an
emission as high as 100 tC ha-1 (from above- and below-ground carbon stocks) this could be
important (Searchinger et al., 2008).
It has been suggested from visual observation of the terra preta that biochar could also lead
to a net stabilisation of other organic matter (Sohi et al., 2006; Lehmann and Sohi, 2008). If
this is the case, this could be another factor benefiting the overall net carbon gain from
biochar-based soil management strategies. This is a particularly intriguing prospect since the
capacity for soils to store biochar, not relying on protective capacity of a limited clay surface
area, is not finite in the way that it appears to be for other soil organic matter. Thus in
addition to representing a carbon store of its own, it is possible that biochar can enhance the
intrinsic soil organic carbon storage capacity of soil by affecting the turnover of indigenous
carbon. However, apparently contradictory data have been published, which seems to
suggest an accelerated decomposition of leaf litter in soil amended with biochar (Wardle et
19
al., 2008). The mechanisms and predictive description are, however, still to be determined
and defined.
A carbon balance for a pyrolysis scenario that appears positive with respect to the
atmosphere in the short term (i.e. a net emission) may be rendered negative if the feedstock
for biochar production comprises a new, additional and sustainably supplied resource. This
resource could derive from a managed increase in the above-ground productivity of existing
crops, or by maintaining vegetation in a state of high net primary productivity through growth
continuous cropping. Maintaining high net primary productivity above ground also promotes
higher productivity below ground, with an associated increase in root exudation and root
turnover. Plant and root productivity can also be enhanced by the use of fertiliser; noting,
however, the overall carbon balance of a strategy based on increasing soil carbon through
increased use of fertiliser. In assessing the carbon balance of a biochar strategy, it is
important to include the carbon cost of transporting feedstock and biochar between field and
pyrolysis facility and vice versa. In the scenario where there is no energy capture from
pyrolysis of organic matter, gains will depend on positive impacts on crop yield and soil
health.
Greatest overall impact on greenhouse gas emissions are likely to be realised where gases
produced during pyrolysis are captured and utilised in a manner that offsets fossil fuel
energy. In comparing a strategy that involves biochar production and its use in soil, it can be
argued that the reference scenario should be the use of the same feedstock in some other
form of bioenergy capture, such as simple combustion or, alternatively, pyrolysis with
gasification or combustion of the biochar by-product.
Bioenergy in general is often described as carbon neutral, since the carbon emitted in the
use of the energy approximates to the amount removed from the atmosphere to create the
feedstock in photosynthesis. For a biochar-based strategy to be carbon-negative, the
avoided carbon emission – or rather CO2 -equivalent emissions (since other greenhouse
gases have to be considered) – from use of 1t carbon in feedstock must exceed 1tC
(Renner, 2007). If it is assumed that the feedstock would otherwise decompose and return to
the atmosphere as CO2, as is the case for organic material added to soil, the carbon
emission from producing biochar and adding the stabilised residue to soil may alone, over a
few years, be close to one unit. Thus, with any net energy capture through use of gases (or
oils) produced during pyrolysis, the technology may be considered carbon negative
(Lehmann, 2007). The indirect effects on carbon emissions resulting from a positive impact
on agricultural productivity, plus an effect of biochar or the emission of non-CO2 greenhouse
gases from soil, may enhance this.
However, the carbon-negative status of the technology has been questioned by Bruun
(2008), who considered the additional fossil fuel offset that could be obtained if biochar was
used for non-energy purposes. Furthermore, biomass pyrolysis itself did not extract more
energy from a feedstock when compared to another bioenergy use. Bruun (2008) also
pointed out that over longer timescales, an increasing proportion of the carbon initially
sequestered in biochar would be slowly returned to the atmosphere through its slow
degradation back to CO2.
In terms of energy captured per unit of CO2 released it may be correct that biochar
production is not associated with less carbon emission than other forms of bioenergy.
However, when expressed in terms of energy captured per unit of carbon in the feedstock,
this is not the case. During pyrolysis the majority of energy embodied in feedstock (about
70%) is converted into combustible syngas, but with the liberation of only half of the
feedstock carbon (Lehmann et al., 2005a). This is because energy rich but less
carbonaceous functional groups are liberated first.
In the pyrolysis of organic wastes and crop residues, the emission avoided in preventing its
natural decomposition in soil, composting or landfill (for example) is an important part of the
overall CO2 -equivalent savings. In the utilisation of non-waste feedstocks, such as biomass
20
crops, there is no such avoided emission. Indirect CO2-equivalent savings resulting from use
of biochar in soil must then exceed the energy embodied in the biochar and allowance made
for the implications of land use.
Since pyrolysis is a more carbon-efficient way to capture bioenergy compared with other
bioenergy systems (in terms of CO2 MJ-1), manufacture and storage of biochar would add
significant benefits for climate change mitigation alone. From this perspective, storage of
biochar does not need to be in the soil, and it had been proposed that entire valleys could be
used as storage facilities for biochar (Seifritz, 1993). However, applying biochar to
agricultural soils is currently the most widely proposed path, since it is more likely to
overcome the opportunity cost in energy production (the recoverable energy forgone in the
biochar). If biochar can provide reliable agronomic benefit it may command a value in crop
production in addition to a potential carbon credit.
However, whilst the potential for management of the terrestrial carbon cycle is the reason for
the current interest in biochar, to be workable a biochar-based scenario must: (1) assess the
monetary value of direct and indirect emission savings arising from the use of biochar
against the opportunity cost of biochar combustion or alternative use, (2) provide certainty,
verification and possibly evidence for carbon-equivalent savings and (3) consider the indirect
costs and benefits to land users and upstream food processors from the use of biochar in
soil. The latter might include the cost of biochar application, weighed against the marketing
benefits gained through carbon-neutral food products.
In short, a full life-cycle analysis of alternative scenarios is required. However, greater
certainty is required on the following in order to fully assess biochar-based soil management
for specific applications: (a) the stability of biochar carbon in soil, (b) the indirect impacts of
biochar on carbon-equivalent emissions and (c) the security, reliability and constancy of price
for pyrolysis feedstocks. These are reviewed in more detail in the next sections.
The potential for technological developments in pyrolysis to enhance flexibility and overall
efficiency is a separate topic, and will be facilitated by its expansion and forums such as IBI,
and national networks such as the Network of Australian and New Zealand Biochar
Researchers, and the UK Biochar Research Centre. It should be highlighted, however, that
from the perspective of the economics of energy capture, the value of biochar and the overall
outcome of the analysis is sensitive to the price of heat and power generated from other
fuels. It is also affected by any subsidy for renewable energy, which may have the effect of
inflating the monetary value of the energy in biochar (Woolf, 2008).
Its extraordinary stability means that charcoal particles in soil have been used as a tool for
dating and paleo-environmental reconstruction as well as evaluation of cropping practices
over centennial and millennial timescales (Ferrio et al., 2006, Scott et al 2000). Studies of the
age of the carbon in terra preta of Brazil, as well as similar black carbon accumulations in the
soils of other natural ecosystems that have resulted from natural fire events, provide
considerable reassurance for the general long-term stability of at least some significant
component of biochar. However, laboratory-based studies using freshly-made char tend to
show some mass loss – sometimes large – in a period of days to years.
The paradox of apparent long-term stability against measurable short-term decomposition
suggests that biochar comprises both stable and degradable components. At the moment
there is insufficient data in the literature to compare the responses between short- and long-
term stability under different climates and in different soils, which could enable the relative
size of these fractions to be assessed.
Combustion conditions during pyrolysis as well as the type of feedstock are probably
influential in determining the proportion of relatively labile components in biochar products.
Measuring the influence is essential for the optimisation of pyrolysis for maximum net carbon
21
stability. In optimising biochar production against energy capture to address climate change
most effectively, a consistent level of stability in biochar is the aim. Maximising retention of
carbon into biochar is counter-productive however, in both carbon and economic terms, if the
additional material is in fact associated with short- or medium-term loss to the atmosphere.
The chemical composition of biochar provides the principal explanation for its generally high
level of stability and is reflected in broad terms by its elemental composition: highly aromatic
and with a very high carbon content. It is likely that its stability is strongly modified by its
physical properties and structure, however. If the biotic and abiotic processes determining
the fate of biochar are the same as those for other soil organic matter, higher soil
temperature, moisture availability, lower clay content and intensive tillage will accelerate
decomposition rate.
The soil system has a remarkable propensity to degrade organic substrates introduced into
it. As a substrate generally very low in the concentration of key crop nutrients, the rate at
which biochar degrades in situ may also be influenced by the exudation of labile, nutrient rich
substances in the rhizosphere. This, in turn, is affected by cropping pattern.
Soils that contain large amounts of char are those that have experienced relatively frequent
natural fires over a period of millennia (Lehmann et al., 2008). Converting a fraction of
standing plant biomass to black carbon in soil constitutes net removal of CO2 from the
atmosphere (Forbes et al., 2006). A relatively minor under-estimation in our estimates for the
percentage converted could explain up to one-fifth of the so-called missing carbon sink, that
is the imbalance between carbon eliminated from forest and fossil fuels, against observed
atmospheric CO2 (Kuhlbusch, 1998).
In natural systems it is not possible to determine the exact amount of biochar added to a soil
over the long-term history and the biochar in these soils will be of disparate age. However, a
loss rate constant can be derived mathematically by assuming that current and historic levels
of standing biomass are representative (Graetz et al., 2003; Mouillot et al., 2005; Forbes et
al., 2006), and a simple factor applied to capture the rate of conversion of biomass to
charcoal in burning episodes. This approach has yielded the best estimates for long-term
mean residence times, which are in excess of 1000 years (Lehmann et al., 2009). Direct
monitoring of archived soils from medium-term experiments seems to support such stability
(Skjemstad et al., 2001).
A portion of black carbon in soils globally also comprises condensed aromatic carbon in the
form of soot particles. This, in turn, can be confused with soot similarly formed in fossil fuel
combustion. Such black carbon is considered to lie at the most stable end of a black carbon
continuum (Masiello, 2004). Over extended timescales the physical transport of this material
through the soil and into water and sediment is inevitable and is seen in its accumulation in
marine sediment (Masiello et al., 1998). This observation highlights the potential to confuse
physical transport of biochar from a trial site for oxidative loss. It also indicates the
importance of such processes to the sequestration of carbon in the natural carbon cycle
(Smittenberg et al., 2006).
Although char from wildfire offers opportunities to study the long-term dynamics of pyrolysed
biomass, the fire and low rate of biomass conversion to char suggests probable differences
in composition and function. Simple charcoal manufacture probably began with the discovery
of fire; therefore, it is not surprising that sites of ancient habitation are associated with soils
enriched in char. Whilst the terra preta provide a neat and convincing example for the
deliberate use of biochar in agriculture, there is circumstantial evidence for its informal use in
other regions, not only in the distant past but in recent centuries (Young, 1804) and in the
current day (Lehmann and Joseph, 2009a).
22
3.1.5.2. Influence of biochar feedstock on stability
In soils where charcoal has been known to be abundant, it is associated mainly with the very
fine, sub-50 µm soil fraction (Brodowski et al., 2006). This suggests that through some
abrasive physical process or the destructive physical impacts of freeze-thaw and shrink-
swell, the initial size of brittle biochar particles may be relatively unimportant to its long term
interactions in soil. Ponomarenko (2001) found biochar evenly distributed across particle size
and biochar particles to become increasingly rounded over time at a rate dependent upon the
abrasiveness of the soil. Ponomarenko (2001) also found the concentration of clay-sized
mineral particles embedded in biochar pores to increase with time and noted that this would
inhibit their isolation using density-based techniques.
Brodowski (2006) found a small proportion of biochar particles in soil to be associated with
micro-aggregates, but for this biochar to account for a rather large proportion of the carbon
that is present in such structures i.e. compared to other particulate organic matter. The
authors used this as evidence for physical protection of biochar against degradation and also
noted that biochar might act as a binding agent for organic matter in aggregate formation.
Although they did not specify whether the latter would be a purely physical interaction or a
consequence of biological activity, Watts (2005) previously found no effect of charcoal on
aggregation at low temperatures designed to preclude biological activity. In an earlier
publication Glaser (2000) found a large proportion of biochar in terra preta to be present in
unprotected fractions. Obtaining similar results, Murage (2007) noted that the misleading
impression might be gained that active soil fractions turn over more slowly in soils that are
enriched in biochar.
Currently there is no published information to demonstrate whether the physical diminution of
biochar in soil is accompanied by oxidative loss of carbon. However, X-ray photoelectron
spectroscopy showed abiotic oxidation (with proliferation of carboxyl groups) to occur in the
porous interior of biochar, whilst biotic oxidation affected external surfaces only (Cheng et al.,
2006). Biotic oxidation might therefore be enhanced as particle size decreases, although in
the study of Cheng (2006) it was also quantitatively less important. These findings have been
further validated (Lehmann et al., 2005b) using synchrotron-based techniques (near-edge X-
ray absorption fine structure spectroscopy).
At the macro-scale biochar products range from powdery to brittle, depending upon the
physical microstructure of the material from which they are derived. Those produced from
woody feedstock display a predominantly xylemic structure that is coarse and strong. These
also display the highest carbon contents, in excess of 70% C and up to 90% C, and are low
in trace elements. Those produced from rye grass, maize and digested feedstocks i.e.
manures are powdery, lower in C (over 60%), and enriched in minerals and nutrients. Thus
the latter are not only less physically recalcitrant, they are also a more attractive microbial
substrate.
Climate determines soil temperature, which affects the rate at which both biotic process and
abiotic reactions occur in the soil. However, in the absence of water the effect of temperature
is irrelevant, as water is essential for biological cell function, and solution phase reactions
proceed by definition only where water is present. Thus synchrony in a conducive
environment of rainfall and temperature and rainfall conditions is required in order to
maximise overall soil activity.
Biochar should modify not only the soil water holding capacity of the bulk soil, but also the
physical location of water within the soil matrix, since the smallest pores become water-filled
first and remain moist the longest (Gaskin et al 2007). The size of these pores makes them
relevant to microbial populations as a physical niche. There is also evidence that mean soil
temperature and diurnal temperature fluctuations are impacted by the effect of biochar on
soil colour (Krull et al., 2004; Oguntunde et al., 2008).
23
The effect of climate on biochar oxidation has been evaluated in a transect study spanning
several climatic zones. Sites along the transect had each received inputs of biochar during a
brief and defined period in industrial history 130 ybp, but received greatly contrasting mean
annual temperatures (Cheng et al., 2008). The accumulation of cation exchange capacity
was correlated to mean temperature and the extent of oxidation was seven times higher on
the external surfaces of biochar particles than in the interior.
The potential consequence of a warmer global climate releasing CO2 through accelerated
mineralisation of black carbon was first scoped by Druffel (2004) who indicated potential
emission rates of 2 to 7 GtC y-1 by 2100. However, if a larger proportion of the global soil
carbon stock comprises recalcitrant black carbon than is assumed in current models, the
more active pools must be smaller and the overall response to warming significantly slowed
(Lehmann et al., 2008). General arguments concerning the relative response of recalcitrant
carbon and more active carbon pools to changing temperature has not been resolved (Fang
et al., 2006).
If, as proposed, natural soil movement influences the breakdown of biochar through its
reduction in size, then the rate of breakdown would be expected to be further accelerated by
tillage. This is important to consider since tillage is perhaps envisaged as the primary means
to incorporate biochar into soil.
Quénéa (2006) reported a 60% decrease in both the soot and charcoal content of sandy soil
under temperate forest during 22 years after conversion to intensive agriculture with annual
tillage. The loss of total soil carbon over the same period was 30%, suggesting that biochar
and charcoal were relatively less resistant to degradation than bulk soil organic matter after
24
disturbance. However, the analysis of the charcoal data was based on larger hand-picked
fragments and it seems likely that particles broken down into very fine fractions might have
led to an overestimate of the loss. The initial soot content was very low. In contrast, 50 years
of cropping and cultivation had no measurable change in the aromatic aryl carbon, taken to
reflect charcoal, whilst other fractions declined rather rapidly (Skjemstad et al., 2001).
More research may enable likely rates of breakdown to be predicted. If, for example, tillage
was a key factor, maximum longevity of biochar targeted by application on land where
minimum tillage is practised. In no-till systems, biochar could be sequestered into soil
through a one-time addition at the time of conversion from a tilled system.
The net carbon gain resulting from stabilisation of carbon into biochar, and its storage in soil,
needs to be refined. There is even less information available for the impact of biochar in soil
on the emission of greenhouse gases other than CO2. The contribution of nitrous oxide (N2O)
and methane (CH4) are major contributors to climate forcing and have significant agricultural
sources, including soils. There is evidence that biochar may suppress the emission of these
gases from soil.
There may be additional indirect benefits in terms of greenhouse gas emissions, resulting
from improved crop production through use of biochar. Although the global possibilities are
currently hypothetical, in an era of falling global grain stocks, the value of biochar could
extend beyond a purely financial consideration for land users and become increasingly
relevant politically and economically. Growing concerns around both energy and food
security may accelerate the development and application of biochar technology and
associated Governmental or inter-Governmental market interventions to support it.
The direct impacts of biochar on crop yield are reviewed in Section 3.2.2.
Where economically optimal fertiliser rates are currently applied, biochar has the potential to
deliver the same crop yield with a lower application rate – with potentially significant
greenhouse benefits. In more detailed assessments for the overall carbon balance of a
biochar strategy (Gaunt et al., 2008), an assumed 10% reduction in the fertiliser required to
maintain current crop yield was found to be a particularly important component of the net
carbon benefit. This reflected the energy intensive nature of nitrogen fertiliser production and
the N2O emissions that result from fertiliser application and use.
The purpose of biochar application might not simply be to attain a greater yield, however, but
possibly to achieve predictability in yield through a lower susceptibility to climatic events such
as floods and drought.
Also, the economic optimum after biochar application could be gained through a gain in crop
yield at the same current or possibly higher rate of application, in which case the net result
would be higher per hectare yields.
Furthermore, biochar could increase, maintain or at least limit gradual decreases in crop
yield on land where soil fertility and productivity is currently in decline. Under changing
climate the benefit of biochar in response to increasingly erratic or intense rainfall events
could be more acute, and/or enable plants to better exploit higher CO2 concentrations. This
suggests a potential role for biochar to assist in adaptation to climate and environmental
change.
These factors would benefit global carbon balance in several very important ways. Firstly it
could reduce the degradation of existing agricultural land, and thus alleviate pressure on
natural systems, which usually represent a significant store of carbon as well as biodiversity.
Maintaining or enhancing productivity of existing land may also make relatively more land
available for bioenergy or other alternative crop production systems.
25
Modelling of these possibilities, at this stage, may not be possible due to too many
uncertainties (economic as well scientific). However, if we view biochar as a technology with
the potential to be practised on a very large scale, they have to be assessed in the long term.
Importantly, they highlight the complexity of the biochar topic and the need to think carefully
about the system boundaries drawn in assessing benefits and impacts.
The global warming potential (GWP) of a gas reflects two aspects: the efficiency of the
molecule in absorbing incoming solar radiation and its rate of chemical breakdown in the
atmosphere. By definition the global warming potential (GWP) of CO2 is 1.0; by comparison
the GWP of nitrous oxide is 310. Under anaerobic conditions N2O is emitted from soil through
denitrification, a process in which specialised microbes that obtain energy from the reduction
of nitrate (NO3-), or intermediate gases, to dinitrogen (N2). However, it appears that nitrifying
bacteria generally involved in conversion of N2 to ammonium (NH4+), i.e. nitrification, may
simultaneously denitrify (Bateman, 2005).
The availability of NH4+ is generally controlled by organic matter mineralisation, which is
climate driven, but its concentration is greatly enhanced by the application of nitrogen
fertiliser or, in livestock and gazed grassland systems, from dung or slurry application.
Regardless of the setting or source, the majority of soil nitrogen is in organic form and N2O
emanates from the utilisation of a relatively small and dynamic nitrogen pool.
Life cycle assessments quantifying the benefits of biochar-based strategies for energy
depend quite heavily on a decrease in the emission of N2O that frequently follows the
addition of mineral nitrogen fertiliser. Accounting for this effect makes a great difference to
the overall analysis of how a biochar to soil strategy impacts on net greenhouse gas balance
(Gaunt et al., 2008). The expectation for this effect relates to the general impact of biochar
on retention of N in the soil in a way that also enhances crop nutrition (see Section 3.1.6.1.).
If the latter effect is surface-mediated, it seems unlikely that biochar confines N to a physical
location – such as very small pores – where it is inaccessible to denitrifying bacteria. It may
be that, instead, biochar inhibits the process by sequestering dissolved mineral N.
Published data demonstrating the effect of biochar on suppression of N2O remains very
limited. In the most widely cited study to date (Yanai et al., 2007) ‘bio-waste’ charcoal was
applied during a re-wetting of a former grassland soil, high in organic matter, in laboratory
incubation (25°). Nine-tenths of N2O was suppressed in five-day emission episodes after
wetting of soils to 73% and 78% water filled pore space. At a slightly higher water filled pore
space (83%), charcoal had the opposite effect, increasing N2O emission. The rate of biochar
addition used in the study equated to a relatively high application rate of 180 t ha-1 in topsoil.
However, the authors were able to exclude the possibility that the alkalinity of their charcoal,
or its nutrient content, were significant factors in their observations.
In an arable soil with much lower C content (2.2 %C), Sohi (2008) has studied the effect of
willow charcoal at a much lower rate of 10 t C ha-1 which were assessed during 20°C
incubation of wet (70% water holding capacity) and re-wetted (from 20% water holding
capacity) soils, with and without simultaneous addition of small amounts of inorganic N
(equivalent 75 kg N ha-1). A more modest suppression of 15% was proportionally similar for
all treatments where there was any response at all (the already-wet soil did not emit
significant N2O). After six months, available soil N would have been largely consumed and
the soils thoroughly equilibrated. A second inorganic N addition (without new charcoal) at this
time showed no difference in N2O emissions between amended and control soils.
If any correspondence exists between the two studies it appears that not only is effect of
biochar on N2O likely to be non-linear with respect to rate of application (and significant but
not large at realistic rates) but – as authors of both papers conclude – the effects are likely to
reflect the impacts of biochar on soil physical properties, particularly modification of pore-size
distribution (of which water holding capacity is not a sensitive measure). In particular the
effect may only be seen during re-wetting, and not when soils are maintained wet. Whether
the benefit upon re-wetting is repeatable remains to be established.
26
Measurements of N2O emission in the field environment are difficult due to the transient and
spatially variable nature of denitrification. Like the studies described in Chapter 3, the
availability of sample biochar in the quantities required to assess its many effects in true
randomised plot designs presents a major challenge. Biochar field experiments with periodic
measurement of N2O in cover boxes is currently in a third year in upstate New York
(<http://www.css.cornell.edu/faculty/lehmann/research/biochar/biocharproject.html>).
In tropical environments field experiments have been established in Columbia and in Kenya.
Results from the Columbian trials indicate 80% suppression of N2O emissions (Renner,
2007).
Methane has a relatively low GWP of 21, but is six times more abundant in the atmosphere
than N2O (1.8 ppm compared to 0.3 ppm for methane), and has an annual flux approximately
50 times higher. Aside from industrial emissions, including natural gas exploitation and
distribution (accounting for about 20%), methane emanates primarily from the soil of natural
habitats and thus, uniquely for the main greenhouse gases, increasing rates of emission
have begun to stabilise. Within agriculture, paddy cultivation of rice and the guts of the
growing ruminant population (primarily grazing domestic animals) are key methane sources
(IPCC-2001,
<http://www.grida.no/publications/other/ipcc%5Ftar/?src=/climate/ipcc_tar/wg1/index.htm>)
Specialised methanotrophic bacteria make most aerobic soils a net sink for methane,
however, and the relatively rapid consumption of methane explains to a large extent its
relatively low GWP. The link between methane consumption and aerobicity is important in
the context of reduced tillage, however. These practices have been widely promoted for their
sequestration of carbon. Whilst higher topsoil organic matter is liable to improve both water
infiltration and holding capacity, increased moisture status is likely to result in a relative
increase of methane emissions (e.g. Castro et al., 1995).
Field experimentation with biochar in Columbia showed the elimination of CH4 emission
(Renner, 2007). A number of studies are currently assessing the impact of biochar on the
emission of methane from paddy soils. At this time there are no results published in the
scientific literature.
The stability of biochar and the biological activity that results from its application are
intrinsically linked, as are soil properties such as clay content, pH and cation exchange
capacity (CEC) and climatic variables.
The ancient terra preta are higher in organic matter compared with adjacent soils that do not
contain black carbon (Lehmann et al., 2003). This has lead to the hypothesis that black
carbon in soil leads to increased stabilisation and hence accumulation of other carbon. This
may provide one of the few mechanisms by which the intrinsic capacity of a soil to store
organic matter can be modified from a management perspective, and if correct, increases the
net carbon gain from the use of biochar.
However, some studies have reported increased microbial activity in soils enriched in biochar
(Steiner et al., 2003; Steiner et al., 2008). Upon addition of biochar to soil for the first time,
mineralisation may be stimulated by the presence of an active fraction and associated
soluble nutrients or labile carbon fractions. It has also been noted that the physical structure
of typical biochar products provides a secure environment for microbial colonies (Ogawa,
1994). However, it should be noted that experiments must be designed such that the system
is correctly monitored, e.g. all soil layers, gaseous losses and plant growth. Currently,
findings to date should be viewed as provisional.
Microbial biomass is not a measure of microbial activity but the abundance of microbial cells.
Thus whilst an increased microbial population associated with increased soil organic matter
27
without any obvious increase in substrate supply may seem paradoxical, it might suggest a
decrease in microbial efficiency, possibly associated with a change in the balance between
different groups of microbes. A simultaneous increase in CO2 emission, however, would
indicate enhanced plant growth and higher inputs of labile carbon via the plant roots.
In soils where char is present naturally in higher concentrations as a result of natural forest
fire or prescribed burning, the microbial community may include specialised species with a
capacity to degrade a relatively scarce and challenging substrate. This may explain the
distinct communities observed in terra preta, but is not clear whether these species are truly
ubiquitous to other soils (if scarce), or whether the capacity for soils to degrade such
materials is acquired over relatively long periods.
Lower bulk density and/or higher organic matter reduce the fuel requirement for mechanical
tillage, which can be managed in few other ways. It may also facilitate the process of
reducing the tillage used in agricultural systems. Soils with higher organic matter content also
tend to display higher water-holding capacity. Thus a further saving in energy costs can
come from reduced irrigation frequency or intensity. Surprisingly little information has been
collected on the impact of biochar on such parameters. However, in Ghana, kiln sites
showed topsoil bulk density approximately 10% lower than in adjacent soils (Oguntunde,
2008).
In addition to the price of biochar, land-users will incur the direct costs of applying biochar to
the soil. There are also potential non-monetary costs associated with the collection of straw
from their land as a pyrolysis feedstock, which affects the readiness of land owners to
engage in the market. In ‘closed’ systems where biochar is returned to the same land that the
feedstock originated, there may be opportunity costs. Currently, no socio-economic studies
exist that would address questions on these matters. However, one key advantage of a
biochar strategy is that, assuming that the provision of key functions is limited only by the
longevity of the biochar, its stability would dictate that annual or even regular applications
would be unnecessary to obtain benefits.
Widespread use of non-waste feedstocks for energy and biochar (or only biochar) could
impact not only commodity prices but, in a manner analogous to that seen with large-scale
bio-ethanol production in the USA, impact on the economics of continued energy production
through feedbacks on land and input prices. This raises complex socio-economic issues that
must be considered (The Royal Society, 2008) and modelled (Rokityanskiy et al., 2007).
Also, as for any assessment of bioenergy systems, it is essential to define boundaries that
spatially allow all possible land-use effects to be assessed, in the context of the overall net
greenhouse gas benefit (Searchinger et al., 2008).
The proximity of a pyrolysis facility to an adequate catchment for feedstock must be
economically and logistically viable, and can potentially affect the CO2 -equivalent savings.
This is the case for biomass and bioenergy facilities generally. However, for biochar the
proximity of suitable locations for biochar application to soil is important as well. If the
gathering of feedstock and distribution of biochar occur over the same area, the logistical and
cost impacts may not be greatly affected. However, it is important to think about biochar
scenarios in a spatial context (Figure 10).
28
Figure 10. Scenario for multi-feedstock production of biochar, and multi-application use,
emphasising the spatial context
Possible off-farm resources include municipal green waste from gardens and parks,
composted or compostable urban waste, digested sewage sludge and mixed municipal
waste. In addition, in the future, by-products of other bioenergy or bio-fuel systems may be
available.
Utilisation of off-farm wastes for biochar production holds the attraction of potential cost
savings from avoiding landfill or other disposal charges. In addition, compared to typical or
existing disposal methods, there may be a lower emission of CH4 and N2O greenhouse
gases than that emanating from direct placement in soil, enhancing the net gain in carbon
equivalents through avoided emissions of high GWP gases. However, many such wastes
have a high water content which will incur increased emissions (and cost) associated with
higher requirement for process energy in pyrolysis.
In a ‘closed loop’ scenario, biochar is incorporated into the same land, or at least the same
enterprise or groups of enterprises, from which the pyrolysis feedstock originates. A typical
scenario would involve utilisation of cereal crop straw that in intensive arable areas is often,
effectively, a waste product. Although there is no published laboratory work to support the
use of biochar produced from wheat straw, there is limited existing information on the relative
stability of biochar from rice husk, sugarcane bagasse and straw from maize. In industrial
agriculture crop straw may constitute 2 t C ha-1. Putting this scenario in the context of the UK
29
example, with approximately 4 M ha of cereal crops grown, annual total fossil fuel CO2
emissions amount to 170 M t.
Theoretical comparisons have been made for the carbon-equivalent gain offered by the
pyrolysis of maize straw versus use of a dedicated biomass crop (Gaunt et al., 2008).
Utilising biomass crops for energy on a large scale has a potential impact on the land
available for food production and may exert new pressure on non-agricultural land use.
Biochar produced from the pyrolysis of biomass crops might be incorporated into different
agricultural land from where the biomass feedstock was grown. This could be for greater
agronomic gain, to apply the product in rotation over a wider area to maximise benefits, or to
deal with the cumulative quantity of product. In the combined energy and bio-oil co-
production case study considered by Ogawa (2006), the biochar by-product was also
returned to adjacent arable land.
Most scenarios considered to date have focused on conventionally managed arable land,
where biochar could be added to soil as part of an existing tillage regime. Biochar could be
incorporated during conversion of land to no-till, but a strategy of integration into no-till and
grazed grassland systems has not yet been considered.
3.1.7.4 Forestry
Ogawa (2006) outlined a scheme for carbon sequestration by forestation and carbonisation.
This scheme revolved around fast growing plantation tree species fixing atmospheric CO2,
with the products comprising not only conventional timber, wood chip, and pulp, but diversion
of wastes and residues to a carbonisation procedure and re-application of this stabilised
carbon back to the plantation soil. This approach has been formally proposed under the
Clean Development Mechanism for a scheme in Sumatra, Indonesia.
In the state of Minas Gervais, Brazil, an existing commercial project claims, under CDM, a
carbon credit for substitution of coal-derived coke for smelting of iron by pyrolysed plantation
eucalypt. The project produces 300,000 t y-1 charcoal. The charcoal ‘fines’ that account for
about 5% of the product are utilised for briquette manufacture rather than application into
soils. In Australia, the potential for integration of oil production from oil mallee trees with
processing of wood waste for production of biochar for use in crop production has been
examined (McHenry, 2009).
Seifritz (1993) evaluated the size and cost of the carbon gain that could be realised by
straight conversion of plantation forest biomass to stockpiled biochar. The scenario included
no capture of energy in the conversion, highlighting instead the net primary productivity that
is maintained by cropping, and the long lifetime of charcoal compared to the nature and fate
of traditional timber products.
In the tropical context, ‘slash and char’ scenarios have been discussed, where one-off inputs
of biochar are made during conversion of land from forest to agriculture (Steiner, 2006), or
perhaps ‘crop and char’, with cycle of positive feedback between one-off, occasional or
rotational inputs of biochar and increasing biomass productivity and feedstock resource. In
both cases, pyrolysis would be performed using the most basic (and perhaps relatively
inefficient) technology such as simple pits of clay kilns. However, as examples of viable,
village-scale bioenergy based on gasification technology in developing countries increase, it
is conceivable that technological development in tandem with increased income from ‘crop
and char’ practices might ultimately realise combined biochar production and energy capture
at the same scale.
In the absence of adequate technological development, charring and manufacture of
charcoal may not offer the same benefits to human health as, for example, the substitution of
existing biomass burning practices for basic but cleaner and more efficient combustion
technology (Wang et al., 1999). Conventional charcoal production may also release methane
and other trace greenhouse gases (Edwards et al., 2003). Sub-micron soot particles
produced by condensation reactions in gas streams from combustion comprise the most
recalcitrant forms (Figure 7) of black carbon but, despite the relatively small quantities of
30
carbon involved, may be having an important impact on the albedo of both the global
atmosphere and ice caps, altering the radiative balance and exacerbating climate change
(Ramanathan et al., 2008). Currently the global emission of soot is predicted to decline as
rural users of biomass in developing countries switch to clean burning fossil sources (Streets
et al., 2004). Charcoal manufacture produces less soot than open burning, but despite the
possible scale of future biochar production, its future contributions to the global soot
inventory has not been formally examined.
Observation shows that wildfires are a routine natural and indeed often essential feature of
many natural grassland, forest and woodland ecosystems, and fire is gradually being
incorporated into global ecosystem models (Thonicke et al., 2001). Fire frequency does not
appear to decrease soil C by affecting plant productivity (Ansley et al., 2006) and may
increase it (Czimczik et al., 2005; Ansley et al., 2006); fire does not destabilize black carbon
already present (Ansley et al., 2006) or only partially in organic boreal soils (Czimczik et al.,
2005). Studies using remote sensing have attempted to quantify the pattern and frequency of
burnings (Seiler et al., 1980) and most estimates suggest approximately 1-5% of standing
biomass is converted to black C (Schmidt et al., 2000; Forbes et al., 2006). This figure is
much lower than the figure previously proposed by Kuhlbusch (1996), who suggested
sequestration into black C during the relatively recent era of forest clearance could explain
up to 20% of the so-called missing carbon sink. A detailed analysis in Australia has
suggested that natural fire might provide a sink equivalent to 8.3 MtC yr-1 (Graetz et al.,
2003).
In fired-affected systems standing biomass remains in equilibrium, viewed over the long
term. However, a modest rate of stable charcoal formation during burning means that the net
result of natural fire is that the carbon content of the wider system, including the soil, should
gradually increase. However, this is a slow process and difficult to measure in the field with
repeated experimental burning (Dai et al., 2005). Given that the net primary productivity of
biomass (60 GtC yr-1) is quite large relative to the soil C pool (1500 Gt) the black C pool
should become dominant in the soil over geological time if this fraction did not degrade at all,
even with occasional fire and a low charcoal conversion rate (Graetz and Skjemstad, 2003).
Thus the fact that soil carbon dynamics can be modelled by postulating a relatively small
inert- or very slow-turnover pool (Falloon and Smith, 2000; Smith et al., 2000) is an indication
that biochar must degrade, at some slow rate, even once transport into water and estuarine
sediments is considered (Schmidt, 2004; Simpson and Hatcher, 2004b; Smittenberg et al.,
2006) and accounted for (Masiello et al., 1998).
The Roth-C soil carbon model explicitly incorporates char as one of its pools (Falloon and
Smith, 2000). The inert pool in the Roth-C soil carbon model represents more than simply
char, but also exceptionally degraded, highly stabilised organic matter (Falloon and Smith,
2000). Radiocarbon dating can be used to experimentally refine the site-specific size of the
inert pool to model total soil carbon. However, estimates for a range of sites where such data
are available has suggested only a general relationship with soil texture (Falloon et al.,
1998). It is likely, however, that long-term field experiments of duration useful in
parameterisation of soil C models will provide the data needed to improve on the char pool in
the model.
It may be significant that one experimental site where the model does not simulate field
measurements well is the site of the Waite plots in Australia, where there is a documented
history of burning (Coleman et al., 1997). Also in Australia, Skjemstad (2004b) demonstrated
that by re-allocating carbon between soil pools according to a direct measurement of char,
the Roth-C model may simulate the trajectory of carbon for a range of soils with similar
burning history.
In addition, new techniques for quantifying char experimentally (see Section 2.2.3.) reveal
that, when applied to a wider variety of sites, observed levels of char were considerably
higher than accommodated by the modelled inert pool (Schmidt et al., 1999; Preston et al.,
31
2006). The implications of this finding for our prediction of climate change feedbacks from
enhanced decomposition will become important, as soil models are increasingly linked into
global climate modelling (Lehmann and Joseph, 2009b).
Unfortunately the most reliable and direct techniques for quantifying char are currently not
sufficiently practical for application at the scale useful to assessing the carbon stock that it
represents, at the relevant (global) scales. However, the development of new spectral
analysis techniques using mid-infrared wavelengths (Section 2.2.3) may lead to an approach
that is both rapid and low cost (Janik et al., 2007).
32
Expectation of increased soil fertility benefits arise from studies of the terra preta that
contains high proportions of black carbon (Haumaier et al., 1995; Glaser et al., 2002;
Lehmann et al., 2003; Lehmann and Rondon, 2006). The evident fertility of the terra preta is
generally attributed to high soil organic matter content – organic matter assists in the
retention of water, soil solution and cations – and the retentive capacity of aged biochar itself
for nutrients and water (Section 3.2.3 and 3.2.4),
The black carbon present in terra preta is thought to originate from partially-combusted
biomass residues derived from a range of anthropogenic activities, including kitchen fires and
field burning. A particularly striking characteristic is a stronger relationship between soil
carbon content and soil CEC in these soils relative to adjacent land, indicating that biochar
comprises a greater proportion of soil carbon (Liang et al., 2006). Since CEC is indicative of
the capacity to retain key nutrient cations in the soil in plant-available form and minimise
leaching losses (Section 3.2.4), this is cited as a key factor where differences in crop
productivity are observed.
High rates of biochar addition in the tropical environment have been associated with
increased plant uptake of P, K, Ca, Zn and Cu (Lehmann and Rondon., 2006). In contrast to
mainstream chemical fertilizer, biochar also contains bioavailable elements such as selenium
that have potential to assist in enhancing crop growth.
There has been much speculation concerning the potential effects of biochar on microbial
activity in soil, which in the context of terra preta has been reviewed in detail by Steiner
(Steiner et al., 2003). Assuming that plant inputs and hence microbial substrate remain
unchanged, enhanced microbial activity alone would diminish soil organic matter. However,
this is contrary to the observation in terra preta, where soil organic matter is generally higher
than in similar surrounding soil (Liang,2006). However, a change in the balance of microbial
activity between different functional groups could benefit crop nutrition, specifically
enhancement of mycorrhizal fungi (Ishii et al., 1994), and this could feed back into higher net
primary productivity and carbon input.
There is relatively extensive literature documenting stimulation of indigenous arbuscular
mycorrhizal fungi by biochar, and this has been reflected in plant growth e.g. Rondon (2007),
Nishio (1996). This literature has been reviewed in some detail by Warnock (2007), who
proposed four mechanistic explanations, of which a combined nutrient, water and CEC effect
was considered most probable.
The majority of currently published studies assessing the effect of biochar on crop yield are
generally small scale, almost all short term, and sometimes conducted in pots where
environmental fluctuation is removed. These limitations are compounded by a lack of
methodological consistency in nutrient management and pH control, biochar type and origin.
Studies in a wide range of climates, soils and crops have been conducted. It is not therefore
possible at this stage to draw any quantitative conclusion, certainly not to project or compare
the impact of a particular one-time addition of biochar on long-term crop yield. Nonetheless,
evidence suggests that at least for some crop and soil combinations, moderate additions of
biochar are usually beneficial, and in very few cases negative.
Glaser (2001) reviewed a number of early studies conducted during the 1980s and 1990s.
These tended to show marked impacts of low charcoal additions (0.5 t ha-1) on various plant
species. Higher rates seemed to inhibit plant growth. In later experiments, combination of
higher biochar application rates alongside NPK fertiliser increased crop yield on tropical
Amazonian soils (Steiner et al., 2007) and semi-arid soils in Australia (Ogawa, 2006). Due to
the year to year variation in climate and its impact on short-term dynamics, results from a
number of field experiments recently set up are, whilst generating data, not yet published.
The nature and mechanistic basis for interactions between crop, soil type, biochar feedstock,
production method and application rate will have to be understood to gain predictive capacity
for the performance of biochar in soil, and open the possibility for large scale deployment.
33
Table 5. Summary of experiments assessing the impact of biochar addition on crop yield
Authors Study outline Results summary
Iswaran et Pea, India 0.5 Mgha-1 char increased biomass
al (1980)* 160%
Iswaran et Mung bean, India 0.5 Mgha-1 char increased biomass
al (1980) * 122%
Kishimoto & Soybean on volcanic ash 0.5 Mgha-1 char increased yield
Sugiura loam, Japan 151%
(1985) * 5 Mgha-1 char decreased yield to
63%
15 Mgha-1 char decreased yield to
29%
Kishimoto & Sugi trees on clay loam, 0.5 Mgha-1 wood charcoal
Sugiura Japan increased biomass 249%
(1985) * 0.5 Mgha-1 bark charcoal increased
biomass 324%
0.5 Mgha-1 activated charcoal
increased biomass 244%
Chidumayo, Bauhinia trees on Charcoal increased biomass by
(1994}* alfisol/ultisol 13% and height by 24%
Glaser (2002) Cowpea on xanthic ferralsol 67 Mgha-1 char increased biomass
150%
135 Mgha-1 char increased biomass
200%
Lehmann (2003) Soil fertility and nutrient retention. Bio-char additions significantly
Cowpea was planted in pots and rice increased biomass production by 38
crops in lysimeters at the Embrapa to 45% (no yield reported)
Amazonia Ocidental, Manaus, Brazil
Oguntunde (2004) Comparison of maize yields Grain yield 91% higher and biomass
between disused charcoal yield 44% higher on
production sites and charcoal site than control.
adjacent fields.
Kotokosu watershed, Ghana
Yamato (2006) Maize, cowpea and peanut trial in area Acacia bark charcoal plus fertiliser
of low soil fertility increased maize and peanut yields
(but not cowpea)
Chan (2007) Pot trial on radish yield in heavy soil 100 t ha-1 increased yield x3; linear
using commercial greenwaste biochar increase 10 to 50 t ha-1
(three rates) with and without N - but no effect without added N
Rondon (2007) Enhanced biological N-2 fixation (BNF) Bean yield increased by 46% and
by common beans through bio- char biomass production by 39% over the
additions. Colombia control at 90 and 60 g kg(-1) bio-
char, respectively.
Steiner (2007) Four cropping cycles with rice (Oryza Charcoal amended with chicken
sativa L.) and sorghum (Sorghum manure amendments resulted in the
bicolor L.) highest cumulative crop yield (12.4
Mgha-1)
Kimetu et al. Mitigation of soil degradation with doubling of crop yield in the highly
(2008) biochar. Comparison of maize yields in degraded soils from about 3 to
degradation gradient cultivated soils in about 6 tons/ha maize grain yield
Kenya.
*source of selected references (Woolf 2008)
34
3.2.3. Soil moisture retention
In soil science the following principles are widely accepted and published (summarised in
Krull et al. 2004): The mineral and organic components of soil both contribute to soil water
holding capacity, but only the latter can be actively managed. Water is held more tightly in
small pores, so clayey soils retain more water. The lower soil bulk density generally
associated with higher soil organic matter is a partial indication of how organic matter
modifies soil structure and pore size distribution.
Many studies where the effect of biochar on crop yield has been assessed have cited
moisture retention as a key factor in the results. Given that the pore size of biochar is
relatively fixed, whereas that of the mineral soil is determined primarily by texture, it may be
expected that charcoal increases available moisture in sandy soil, has a neutral effect in
medium textured soils, and decreases available moisture in clayey soil. Any effect of biochar
particle size may be short-lived, as it appears to physically break down into fine fractions
relatively quickly (Section 3.1.5)
Experimentally, the usual technique for assessing pore size characteristics is the moisture
release curve, which indicates how quickly soil moisture is drawn from a soil under
increasing tension. The method is well suited to discriminating differences between soils of
contrasting texture, but its sensitivity may be less satisfactory for discriminating the effect of
contrasting management at one specific location: high levels of replication may be necessary
to show a significant impact of a management intervention of realistic magnitude.
In a more recent study (Gaskin, 2007), moisture release curves were determined using
samples of loamy sand soil from a field experiment where biochar had been added at rates
up to 88 t ha-1. For soils where biochar was added at rates up to 22 t ha-1 there was no
difference compared to non-amended soil, but at the highest rate the difference was
significant at water potentials in the range 0.01–0.20 MPa. At the highest potential the mean
volumetric water content impact was doubled by the biochar addition.
Soil temperature, soil cover, evaporation and evapotranspiration affect available water in soil.
Comparison of actual volumetric water content between biochar-amended and control soils
in field experiments may therefore be confounded by any indirect effect of biochar on plant
growth and soil thermal properties.
Soil organic matter increases soil water holding capacity and in the biochar-enriched terra
preta with their associated higher levels of soil organic matter, Glaser (2002) reported a
water retention capacity that was 18% higher than in adjacent soils in which charcoal was
low or absent. This was likely a combined effect of the char itself and the higher levels of
organic matter that this promotes (Section 3.1.6.4).
There are several reasons to expect that biochar might decrease the possibility of nutrient
leaching in soils, and enhanced nutrient cycling has been cited in various field studies for
positive impacts on yield. However, very few studies have demonstrated the effect or
attempted quantitative description of the mechanism.
In general, the mineral and organic fractions of soil can both contribute to overall CEC, which
affects the ability for soils to buffer periodic flushes of ammonium that result from application
of chemical fertilisers or manures, or bursts of organic matter mineralisation during
favourable, seasonal conditions. The adsorption of ammonium ions is a relatively loose
association that does not necessarily prevent plant acquisition, yet greatly mitigates the
potential for leaching loss and the diffuse pollution issues of drinking water quality and
eutrophication of riverine and estuarine water bodies. Since considerable fossil energy is
35
required to fix nitrogen into fertiliser (Section 2.1.3.6), a low ratio of fertiliser nitrogen
application to crop nitrogen uptake can impact the overall carbon balance of agricultural
activities (see Section 3.1.6.1). Higher fertiliser use efficiency should lead to a lower fertiliser
requirement per unit yield and usually lower nitrous oxide emission (Section 3.1.6.2).
Only certain mineral constituents of soil contribute to CEC on account of abundance, and
hence surface area, and mineralogy, with certain types of clay being most important. On a
mass basis the exchange capacity of soil organic matter may be greater than for any clay
(and up to 50 times greater), but it is a relatively small proportion of soil mass in most
agricultural situations, particularly under tropical conditions. Given these factors, heavy
textured soils under climates that favour higher levels of organic matter show the highest
contributions of organic matter – about one-third – to total soil CEC (Stevenson, 1982). Since
mineralisation of organic matter is a major source of ammonium release in soil, attempts to
raise soil organic matter by increasing rates of input may not decrease – and can potentially
increase – leaching losses. In addition to the chemical stabilisation of nutrients, the physical
structure of soil determines its capacity to hold water, and hence soil nutrients in solution
(Section 3.2.3 above).
There are several reasons to expect that biochar might modify leaching potential in soils.
Available evidence suggests that on a mass basis, the intrinsic CEC of biochar is
consistently higher than that of whole soil, clays or soil organic matter. An analogy may be
drawn to the extreme CEC of activated carbon, which is relevant to its function as a sorption
medium for decolourisation and decontamination. Since secondary thermal treatment of
charcoal is one means of carbon activation, it is not surprising that the process parameters
impact the CEC of primary biochar products with temperature increasing this property
(Gaskin, 2007). This is a function of both enhanced specific surface area and the abundance
of carboxyl carbon groups that they display. The indirect affect of biochar that may result
from its modification of soil pH has not yet been included in most studies by, for example,
applying lime to the control soil.
Whilst determination of CEC and water release curves in homogeneous materials such as
biochar should be straightforward, it is more complex to quantitatively determine the
contribution of biochar once added to soil. Furthermore, the observation that CEC of biochar
may develop over time through both abiotic and biotic modification of its surfaces (Cheng et
al., 2006) implies that in order to develop a predictive, quantitative understanding, methods
to recover aged biochar from soil is required.
Information on the CEC of pyrolysis products is limited mainly by the availability of materials
produced from a sufficiently diverse range of feedstock under different production conditions.
Information on the CEC of char naturally present in soils is limited by isolation methods, so
available studies tend to rely on a comparison of whole soils amended and non-amended
with biochar (Lehmann, 2003; Liang, 2006).
The second mechanism for mitigation of leaching relates to the physical retention of soil
water, which may be enhanced by biochar in coarse-textured soils and any indirect effect of
biochar on the accumulation of soil organic matter (see previous, Section 3.2.3).
The inherent stability of biochar confers a distinction between the CEC benefits that are
possible compared to other soil organic matter; importantly there is no immediate constraint
to the level that can be attained by repeated addition, so in principal this capacity could be
incrementally enhanced. Provided that biochar is biologically stable (Section 3.1.5), the
benefit of higher CEC may be obtained without the risk of contributing to seasonal flushes of
nitrate.
The possible contribution of modified soil water dynamics and CEC to the apparent effects of
biochar on nitrous oxide emission were discussed in Section 3.1.6.2. In addition to mitigating
greenhouse gas emissions, limiting gaseous nitrogen loss can be relevant to crop fertiliser
requirement.
A beneficial impact of biochar on the plant-available phosphorus has been observed in soils
enriched with biochar, which in contrast to ammonium, is not a characteristic generally
36
associated with soil organic matter (Lehmann, 2007b; Steiner et al., 2007). In the context of
nutrient availability, the impact of biochar addition on pH may be important.
Biochar may offer benefits in reducing diffuse pollution originating from agriculture through
deployment in soils from which polluting elements arise. It may also be possible to utilise its
sorptive capacity to remove contamination in the water treatment process. Studies that
demonstrate the capacity for biochar to remove nitrate (Mizuta, 2004) and phosphate
(Beaton, 1960) in this context have been cited, and in by-passing the complexity of the soil
system, controllability is achieved. However, whilst biochar may loosely hold nutrient
elements in a plant-available form, the by-product of water treatment could also be
contamination by toxic organic compounds in wastewater; biochar also has an affinity for
organic compounds (Kookana, 2006). This could confound use of the post-treatment biochar
product on land; the economic and overall carbon and environmental gain to be achieved
from centralised versus diffuse deployment for management of water quality have yet to be
assessed. The precedent for a centralised approach is the current use of activated carbon for
the removal of chlorine and organic chemicals such as phenols, polychlorinated biphenyls,
trihalomethanes, pesticides and halogenated hydrocarbons, heavy metals, and organic
contaminants (Boateng 2007). It is not clear whether the higher surface area and sorptive
capacity resulting from activation of biochar from agricultural crop wastes (Zanzi, 2001)
results in significant differences compared to biochar.
Charcoal production and use appears engrained in many cultures and the apparent success
and longevity of the civilisation that created the terra preta provides some reassurance as to
the long-term safety of biochar incorporation to soil. Currently in Japan, a strong tradition in
the use of charcoal as an authorised soil improver for horticultural and agricultural
applications means that 15,000 t of carbonized material is annually applied to soil (Okimori et
al., 2003).
Nonetheless, a critical and non-prescriptive experimental analysis of risks that might arise
from the deployment of biochar has not been undertaken according to modern criteria, taking
into account all risks associated with production, distribution and physical application of
biochar, as well as its impacts in the soil. The analysis must also be based around products
of slow and fast pyrolysis, rather than simply biomass carbonisation.
This assessment is critical for three reasons: the irretrievability of biochar once added to soil,
the apparent general permanency of biochar once in the soil and the scale and speed at
which the strategy needs to be implemented to contribute to climate change mitigation. In
addition, the issue of responsibility and liability with respect to large scale application to land
is an impediment for companies seeking to invest in the production of biochar or the sale of
food products from treated land, as well as being a moral and political issue for Government
and regulatory bodies.
To date, available information is focused on the two classes of toxic compounds that are
associated most often with combustion processes, namely PAHs and dioxins. Dioxins
predominantly form at temperatures in excess of 1000°C and there are no published studies
to confirm their absence in biochar products (Garcia-Perez, 2008).
The proliferation of PAH in secondary pyrolytic reactions above 700°C is well established
(Ledesma et al., 2002), but smaller quantities may form in the temperature range of pyrolysis
reactors (Garcia-Perez, 2008). Unpublished analyses of several biochar samples also found
a PAH content no greater than that of bulk soil (Manning, pers. comm.); a single published
study examined the full PAH profile (40 individual PAH compounds) in a number of synthetic
char samples manufactured at relatively high heating rate concentrations (Brown, 2006).
Total PAH concentration was 3–16 μg g-1, depending on peak temperature, compared to
28 μg g-1 in char from a prescribed burn in pine forest. Information contained in PAH may
37
provide a measure of thermal history (Brown 2006), but empirical relationships to relate them
to process parameters have not been defined.
The above analyses determine principally the total initial content. It is not clear over what
timescale these compounds are altered in the soil, and most importantly, the bio-available
component in soil is not known. However, it has been stated by Ahmed (1989) that whilst
biochar should contain systems of PAH, existing evidence indicates that no leachable PAH is
present.
No results of bio-assays using biochar in soil have been reported, nor have the appropriate
biochar concentrations been defined in the context of the accumulations that might occur in
water and marine sediments.
38
employed on recreational land or on sports turf. Such applications may increase recognition,
but will not provide the extent of use required to contribute to climate change mitigation.
Currently, uncertainty around the expected benefits and potential returns at current prices is
likely to limit widespread use in mainstream agriculture. This uncertainty stems from
inadequate understanding or quantitative description of the underlying processes and the
multiplicity of potential benefits and interactions.
Key biochar characteristics will vary according to the nature of the agricultural management
system, soil and climate, and may not be static over time. The number of useful biochar
properties and their relative importance will vary accordingly, but at the moment the
understanding necessary to produce biochar optimised to deliver a particular balance of
properties – especially in tandem with viable energy capture – does not yet exist. The
complexity and diversity of decision making on farms, and the susceptibility of soil
management strategies to commodity prices and external economic forces is important too.
To date, assessments of the benefits to be derived from applying biochar to soil have been
made on the basis of very limited experimental evidence, and are often scoping studies
based on generalised situations. The sensitivity of proposed scenarios to the spatial
dimension presented by climate is improving but still inadequate in predictive terms.
Comprehensive, whole-system life-cycle analyses (LCA) with full accounting are required in
order to avoid unintended negative consequences. In such analysis it will be recognised that
deliberate accentuation of one biochar characteristic may impact on the delivery of others, for
example porosity versus nutrient value. Thus not only does the predictive capacity for
biochar ‘performance’ not currently exist, but the feasibility of optimising multiple useful
characteristics is not known. This is inhibiting realisation of other benefits to the wider
system.
In the financial evaluation of biochar technologies it is important to consider not only current
prices, which are known or can be determined, but also their likely future value. Given the
current trajectory of global greenhouse gas emissions, the price of emissions as a tradable
commodity will be increasingly important. The future price of fossil fuel and subsidy levels for
renewable energy are difficult to predict. However, the indirect gains from the use of biochar
will probably increase with the future price of fossil energy, reflecting the generally energy-
intensive nature of the key inputs associated in mechanised agriculture, and possibly with
finite supply of water (irrigation costs). There will be a corresponding increase in value of the
residual energy in biochar as fossil energy prices rise. The price of bioenergy may also be
enhanced by Government subsides designed to improve energy security and promote
environmental goals. In many industrialised countries the opportunity cost associated with
using biochar in soil is artificially enhanced by renewable energy subsidies. The future price
of grains and other commodities is difficult to predict, but changing diet, a growing global
population, and increasingly limited supply of new agricultural land is likely to increase
demand relative to supply.
39
‘avoided emission’ of CO2 has not been presented, although this is a current activity within
the International Biochar Initiative.
Additional evidence for the portion of biochar that can be considered stable over the long
term is required. Furthermore, research is required to determine whether the carbon-
equivalent benefits of biochar application to soil extend beyond direct carbon sequestration
or the avoidance of other greenhouse gas emissions. At the moment these effects are not
fully understood or proven in the predictive sense, nor have the timescales over which they
mainly occur been established (Section 3.1.5.). However, the existence of a current
methodology for stabilisation of organic matter in avoidance of methane emission represents
an important precedent (UNFCCC).
Various national Governments have implemented carbon trading schemes in order to meet
emission reduction commitments under the Kyoto protocol. This has resulted in the
European Union Greenhouse Gas Emission Trading Scheme and subsidiary schemes such
as the UK Emissions Trading Scheme. More recently, Australia has announced plans for a
Carbon Pollution Reduction Scheme (Anon, 2007c).
In these countries, their regional neighbours and in the USA there is a strong market for
voluntary carbon trading carbon. Individuals or organisations engage outside of Government
requirements in a market currently valued in excess of USD 30 billion yr-1. Offsets traded in
the voluntary market are unregulated, and their credentials have been questioned. Biochar-
based schemes should offer the opportunity to trade a more demonstrable offset (by virtue of
the visibility and durability of biochar in soil), that has community as well as climate benefits
through its impact on agriculture. However, there is an expectation within some NGOs that
the inclusion of biochar into any carbon trading scheme will ultimately lead to large projects
based around dedicated biomass crops that will not benefit agriculture and put additional
pressure on rural livelihoods in developing countries as a consequence of land acquisition.
Other major NGOs have not yet adopted a specific position on biochar.
Alongside the IBI, pressure groups such as the US-based Clean Air Task Force have been
promoting biochar based offsets alongside other bioenergy schemes for trading in all carbon
markets (Baum et al., 2006).
40
exist. Providing a measure of certainty to the many possible benefits is a key challenge to be
addressed by further research.
4.5. Research
To date there are a limited number of examples of large-scale publicly funded research
initiatives that assess the use and optimisation of biochar for use in soil. In New Zealand the
Massey University has a Biochar Research Initiative. In the UK the Engineering and Physical
Sciences Research Council supports two established projects, one building capacity in
technology for fast pyrolysis (as part of a wider bioenergy initiative, SUPERGEN) and testing
by-products in soil, and the other developing Carbon Sequestration and Capture technology.
Brazil has funded second and third tier levels within ‘macro-programs’ defined by the
research organisation, EMBRAPA. These will extend field experimentation to create new
terra preta (terra preta nova). At Federal Government level, the US has created the Farm Bill
that supports ‘biochar research development and demonstration’ which seeks to enhance
agricultural energy programs (Anon, 2007b). Biochar was specifically mentioned in the
Garnaut Climate Change Review in Australia (Garnaut, 2008) and has been raised in
Environment Select Committee discussions in the UK.
Currently much of our understanding of the long-term dynamics of biochar is based on
studies of charcoal from natural fire, new charcoal produced using traditional methods or
analogous procedures undertaken in the laboratory. Studies in Brazil use charcoal fines
(waste) from industrially produced charcoal. However, only a small number of
comprehensive studies using the products of commercial bioenergy plants currently exist,
and although the conditions used to produce these products has been guided by preliminary
studies, those conditions may not have been optimised for the soil into which they have been
incorporated. The only full-scale field trials using biochar from slow pyrolysis energy plants
are being conducted in NY, USA
(<http://www.css.cornell.edu/faculty/lehmann/research/biochar/biocharproject.html>).
.
41
5.1. Fundamental mechanisms
The fundamental mechanisms by which biochar could provide beneficial function to soil and
the wider function of the agro-ecosystem are poorly described in terms of providing the
predictive capacity that is required.
In short-term experiments of months to a few years, biochar addition seems to generally
enhance plant growth and soil nutrient status and decrease N2O emissions. Yet surprisingly
little is yet published concerning how these benefits occur, or particularly why the effects are
quantitatively so variable according to crop, soil and application rate. Soil-biochar dynamics
need to be investigated. The required understanding will have to be obtained in the following
areas:
a) Functional interactions with soil microbial communities. Biochar may modify the
symbiotic relationships that exist in the rhizosphere, that is between plants and microbes
in close proximity to the root. At the moment the net effect of physical protection provided
to microbial colonies, and adequate access of the same colonies to labile and soluble
carbon substrates is not yet known. The component of biochar stability provided by
association of individual biochar particles and fine mineral particles has not been
established, and the role of microbial and rhizosphere secretions in promoting them will be
important. Fundamentally, the apparent conflict between high stability, soil organic matter
accumulation and apparent enhancement of soil microbial activity needs to be resolved.
Useful methods will separate indirect effects of increased water holding capacity or altered
water release characteristics, pH effects, and allow for their potentially transitory nature.
b) Surface interactions. It seems that as the exchange capacity of biochar surfaces
develops over time, the contribution of feedstock and production parameters to the
trajectory of its development will need to be established. Once the relative importance of
biotic and abiotic processes in promoting this development are known, and the net effect
of any simultaneous change in the ratio of external- to internal-surface resulting from
physical disintegration under soil movement quantified, the net effect of climate might be
predicted. Interaction of biochar with anions, most importantly phosphate, needs to be
established, and the extent to which nutrient effects are internal, i.e. derived from within
the biochar (finite), and external, supplied by the wider soil, must be determined.
c) Nutrient use efficiency. Understanding the link between biochar function and its
interaction with nutrient elements and crop roots may enable fertiliser use efficiency to be
enhanced and diffuse pollution of watercourses and wetlands.
d) Soil physical effects. The intrinsic contribution that biochar can make to the wetability of
soil, water infiltration, water retention, macro-aggregation and soil stability is poorly
understood – yet should be of critical importance in tropical environments in combating
erosion, mitigating drought and nutrient loss, and in general to enhance groundwater
quality. The loss of biochar through vertical or lateral flow is not well understood; only
recently have studies been initiated to examine movement down the soil profile.
e) Fate of biochar. The stability of biochar carbon is intrinsic to fulfilling its role as a
significant CO2 sink, but in order to perform an agronomic role, it must also remain within
the soil to which it is applied. The environmental role or impact of biochar once it has
moved through a soil profile, or into watercourses, is yet to be assessed. Information on
the extent to which physical breakdown of biochar changes the balance in its properties,
particularly with respect to soil water dynamics, exchange capacity and soil micro-and
macro-aggregation is lacking. Methods are urgently required to assess the long-term
biological stability of specific biochar samples, possibly extrapolating from the dynamics of
atypically high initial rates of decomposition.
f) Impacts on soil N2O and CH4 emission. Published data for the effect on trace gas
emission is extremely limited, but has a potentially great impact on the net benefit of a
biochar strategy. Good predictive models will be necessary for this to be reflected in future
42
accounting for biochar projects, and at the moment there is not a clear mechanism for the
effect.
g) Plant physiological responses to biochar ultimately dictate impacts on growth and yield
and need to be directly targeted in future work.
43
5.3. Carbon cycle modelling
Two types of carbon modelling are required: static spreadsheet models to compare
alternative scenarios for their relative carbon-equivalent gain, and mechanistic soil simulation
models that capture information from short term experiments to predict longer-term impacts
on soil function. In addition, socio-economic models that incorporate a spatial dimension are
required to assess the workability of particular scenarios.
a) Modelling net carbon gain. So far only generic, theoretical analyses have been
published. Full assessment spreadsheet models based on improved experimental
evidence are required to conduct ‘what-if’ comparisons of alternative strategies for
specific feedstock streams and pyrolysis facilities, taking the spatial dimension of
feedstock supply and biochar use into account.
b) Mechanistic soil modelling. Modelling of the linked carbon and nitrogen cycles in soil
with and without intervention using biochar is essential to understanding the fundamental
mechanisms referred to above, and the impact on soil-based emissions of greenhouse
gases. Modelling of soil carbon currently relies on conceptual pools, and essentially
ignores black carbon from a mechanistic perspective. Progress in this area is dependent
on improved quantification methods for biochar in soil.
c) Economic models. Conceptual and actual geographic boundaries must be carefully set
when assessing a particular scenario, accounting for the entire supply chain. Socio-
economic constraints relevant to the application of biochar must be recognised.
d) Audit. A standard methodology for validation and audit of biochar application is required
that ideally permits the source of a particular biochar application to be confirmed
retrospectively.
e) Databases. International support for a global system that enables optimal biochar
products to be selected for application in a particular location and system. The only such
database initiated to date is CharDB, at Terra Carbona
(<http://terracarbona.org/chardb/>).
5.4. Beneficiaries
Pyrolysis enterprises. In areas where biochar may be produced for agricultural or
environmental gain rather than energy production, NGOs may be interested in exploring the
pyrolysis biochar technology. Market development would facilitate the dialogue between
producers and investors as well as researchers and users. Currently the amount of biochar
available for use as a soil amendment (and hence carbon sequestration) is limited to an
extent where even assessment of products for non-energy use is limited.
Charcoal producers. Traditional producers may experience expansion in the market for
charcoal if its use as a soil amendment is supported by land-users for carbon sequestration
or enhancing soil fertility. There is a precedent for charcoal being produced on a commercial
scale within Europe, with almond charcoal supplied to power companies in Spain.
Water companies. Larger scale production of activated charcoal from pyrolysis-derived
biochar could reduce costs. Large scale use of biochar on agricultural land in intensively
farmed areas may also reduce diffuse pollution and the need, and hence costs, for treatment
of water.
Land users. Individual farms or farming consortia would benefit due to greater profitability as
a result of savings on energy and fertilisers. Remediation of degraded or contaminated land
using biochar could be supported through Government, engaging the agricultural community
and supported by environmentally-oriented incentives and subsidy.
44
5.5. Commentary on likely barriers to the adoption of a large scale
enterprises utilising Biochar
If the technical limitations described above are addressed and if biochar-related techniques
are judged to be viable methods to address climate and agricultural problems, then it is likely
that additional barriers to widespread adoption will remain. This section provides a
commentary on these barriers.
The economics of biochar production will be fundamentally altered once methodology has
been proposed and adopted with regard to carbon offset values, in the voluntary market, and
as a longer-term possibility, certification under the United Nations Framework Convention on
Climate Change (UNFCCC) clean development mechanism (CDM).
A streamlined regulatory framework may be essential to avoid stifling initial interest in the use
of biochar products in mainstream agriculture. Government policies to help ensure continuity
of feedstock supply to pyrolysis enterprises could assist in establishment of the industry;
subsidy arrangements could be adopted that favour rather than discriminate against the use
of biochar in soil.
A routine standard method to quantify biochar in soil is essential to realise the research
agenda. Supply of biochar material from commercial pyrolysis facilities is currently extremely
limited and localised, inhibiting research activity. Biochar is highly heterogeneous, so
standards and quality control need to be defined and certified.
Association of pyrolysis with wider bioenergy technology and specifically the biofuel debate
presents an image problem in the wake of diminished global grain stocks and rising
commodity prices. However, this could also present forums where the principle and multiple
benefits of biochar-based strategies can be discriminated and promoted.
The multi-disciplinary nature of the biochar concept seems to inhibit large-scale funding of
the extensive research agenda, particularly the large sums required for long term trials. It
also appears that assigning responsibility for researching biochar within Government and
between public and private sectors is challenging. Funding for testing commercial products
may be borne by companies producing the products, but such activities will need to be
integrated with public sector science to address the wider climate change agenda.
45
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56
World Journal of Agricultural Sciences 3 (5): 572-575, 2007
ISSN 1817-3047
© IDOSI Publications, 2007
Response of Broiler Chickens to Wood Charcoal and Vegetable Oil Based Diets
Abstract: An experiment was carried out to determine whether Wood Charcoal (WC) would affect growth
performance, carcass characteristics and blood profiles of broilers and to determine whether Vegetable Oil (VO)
supplementation would influence similar parameters in broiler chickens fed WC. Dietary WC was incorporated
into broiler starter and finisher diets at 0, 2.5, 5.0 and 7.5% levels while diets containing 2.5 and 5.0%WC were
each supplemented with 1.5%VO to make six dietary treatments. Results showed that feed intake (F1) was
significantly increased in broilers fed 5% WC with or without VO while birds on other diets had similar (p>0.05)
intake. Body Weight Gain (BWG) and feed conversion ratio (FCR) were significantly better (p<0.05) on birds
fed without WC compared to those fed on WC based diets. Supplementation with VO only gave marginal
improvement on performance indices when compared with the corresponding WC based diets without VO.
However, the performance criteria used (F1, BWG and FCR) were still not commensurate to the control diet.
Carcass yield, liver, spleen and kidney did not show any major variations (p>0.05) among dietary treatments
while lung, heart and gizzard indicated significant differences (p<0.05). The packed cell volume, haemoglobin,
red blood cell and white blood cell, MCV, MCH, MCHC values obtained for the six treatments were not
statistically (p>0.05) different from each other. The present study appeared not to justify the dietary inclusion
of WC in broiler chicken diets and its use in broiler diets is not recommended.
Key words: Wood charcoal % vegetable oil % broilers % growth performance % carcass yield % hematology
Corresponding Author: Dr. A.A. Odunsi, Department of Animal Production and Health, Ladoke Akintola University of
Technology, P.M.B. 4000, Ogbomoso, Nigeria
572
World J. Agric. Sci., 3 (5): 572-575, 2007
Table 1: Composition and nutrient contents of broiler starter and finisher diets (%)
Starter diets Finisher diets
---------------------------------------------------------------------------------- ----------------------------------------------------------------------------------
1 2 3 4 5 6 1 2 3 4 5 6
Ingredients 0 2.5 5.0 7.5 2.5+VO 5.0+VO 0 2.5 5.0 7.5 2.5+VO 5+VO
Maize 52.7 49.7 43.7 47.7 47.8 44.9 58.4 55.4 53.4 49.4 52.5 49.5
Groundnut cake 30.6 31.1 31.6 32.1 31.5 32.0 25.4 25.9 26.4 26.9 27.3 27.8
Wood charcoala 0.0 2.5 5.0 7.5 2.5 5.0 - 2.5 5.0 7.5 2.5 5.0
Vegetable oil - - - - 1.5 1.5 - - - - 1.5 1.5
Fish meal 5 5 5 5 5 5 2.5 2.5 2.5 2.5 2.5 2.5
Wheat offal 8 8 8 8 8 8 10 10 10 10 10 10
Bone meal 2 2 2 2 2 2 2 2 2 2 2 2
Oyster shell 1 1 1 1 1 1 1 1 1 1 1 1
Salt 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Methionine 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Premix 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25
Analyses
Dry matter 91.8 91.8 91.8 91.8 91.7 91.8 91.3 91.5 91.6 91.3 91.5 91.2
Crude protein 22.9 22.8 22.9 22.9 22.9 23.0 19.3 19.4 19.6 19.5 19.4 19.5
Ether extract 8.79 8.73 8.66 8.59 8.68 8.57 5.64 5.35 5.47 5.31 6.38 6.74
Crude fibre 3.46 3.50 3.52 3.56 3.46 3.49 4.84 4.05 4.25 4.65 4.28 4.15
Crude ash 3.47 3.66 3.86 4.05 3.67 3.86 2.85 2.96 2.39 3.14 2.94 2.59
NFE 53.2 53.1 52.9 52.7 53.0 52.9 59.5 59.8 58.6 58.6 58.4 58.2
Wood charcoal contains ( %); DM, 94.6, CP, 1.96; EE, 1.08; CF, 9.75; Ash, 15.4, NFE, 64.41
a
Farm Support Services, Ibadan and fed a commercial cut-up parts and organs were separately weighed and
broiler starters mash (24%CP/2900 ME kcal/kg) for 1 week. expressed as a percentage of dressed weight. Blood
Subsequently, one hundred and eighty birds were samples were collected on the 63rd day of the trial from 3
weighed and randomly allotted to the six dietary birds per treatment during slaughter. The samples were
treatments in triplicate lots of 10 chicks each using the collected in bottles containing ethylene tetra-acetic acid
completely randomized design. (EDTA) as anticoagulant. They were then taken to the
The six experimental starter and finisher diets were laboratory for hematological analyses that included
provided to the birds during the starter (1-5 weeks) and Packed Cell Volume (PCV), erythrocyte (red blood cell),
finisher (5-9 weeks) phases respectively. The groups were leucocytes (white blood cell) and haemoglobin. The Mean
kept in a floor-littered poultry house situated at the Cell Volume (MCV), Mean Cell Haemoglobin (MCH) and
University Teaching and Research farm, Ogbomoso. Feed Mean Cell Haemoglobin Concentration (MCHC) were
and water were provided ad libitum. Other routine calculated. The hematological parameters were determined
management practices such as vaccination, drug as described by Davice and Lewis [2].
administration and maintenance of cleanliness in and out The proximate compositions of wood charcoal
of the poultry house were applied. and experimental diets were determined according to
Initial body weights of the birds were taken on AOAC [1]. Data collected were analyzed by analysis of
replicate basis at the start of the study and thereafter on variance technique and the Duncan’s multiple range
weekly basis. Weekly feed intake was also recorded. The technique was used to detect differences among treatment
mean daily weight gain, daily feed intake and feed to gain means [8].
ratio were thus calculated from the data obtained during
the starter, finisher and overall experimental period. On RESULTS AND DISCUSSION
day 63, 2 birds of mean weight close to the average group
weight were randomly selected from each of the 18 The growth performance data of broiler chickens fed
replicates and starved of feed for 12 hours in order to wood charcoal based diets supplemented with or without
empty their crops. The birds were exsanguinated, vegetable oil during the starter, finisher and overall
defeathered, eviscerated and dressed. Each bird’s carcass, experimental periods is shown in Table 2. At the starter
573
World J. Agric. Sci., 3 (5): 572-575, 2007
Table 2: Effect of providing wood charcoal and supplemental VO on growth, performance of broilers at starter, finisher and the overall experimental period
Variable Control 2.5%WC 5%WC 7.5%WC 2.5%WC+VO 5.0%WC*VO SEM
Days 7-35
BWG (g/b) 20.5a 19.5a 22.4a 17.3b 22.2a 21.4a 0.95
Feed intake (g/b) 48.6b 50.9b 54.0a 49.0b 50.5b 51.0b 1.44
FCR(F1/BWG) 2.37c 2.61b 2.41c 2.84a 2.73b 2.38c 0.46
Days 35-63
BWG 50.3a 44.5b 42.6b 41.8b 44.7b 44.5b 1.30
Feed intake 129.2b 127.9b 135.4b 122.4c 127.4b 132.3a 2.55
FCR 2.57c 2.87b 3.18a 2.93a 2.84b 2.97a 0.12
Days 7-63
BWG 35.3a 32.0b 32.5b 29.6b 33.5b 33.0b 0.60
Feed intake 88.8b 89.4b 94.7a 85.7c 88.8b 93.2a 2.06
FCR 2.52b 2.791b 2.91a 2.90a 2.65c 2.68c 0.07
a, b, c: Means within a row with similar superscripts are not significantly different (p>0.05)
Table 3: Effect of dietary charcoal wood on carcass weight, carcass yield, cut-up parts and organ weights of broilers
Diets
----------------------------------------------------------------------------------------------------------------------------------------------------------
0%WC 2.5%WC 5%WC 7.5%WC 2.5%WC+P0 5%WC+P0
Variable 1 2 3 4 5 6 SEM
Carcass
Carcass weight (g/b) 1445.3a 1260.4b 1303.1ab 1155.3c 1470.8a 1387.9a 28.02
Carcass yield (% ) 73.1a 70.3a 71.6a 69.7b 78.4a 75.1a 0.34
Abdominal fat (%) 0.95a 0.65b 0.61b 0.54c 0.69b 0.71b 0.09
Relative cut-up parts (% of CW)
Wing 12.7 12.6 11.4 11.5 11.8 11.5 0.79
Thigh 19.2 16.7 22.9 19.2 19.0 17.1 0.30
Drum stick 14.6 13.7 14.8 15.1 14.7 15.7 0.47
Breast 25.3 25.3 27.6 25.1 24.4 24.5 0.35
Back 18.9 21.4 19.4 19.2 19.9 20.8 0.24
Neck 6.96 6.96 6.90 7.03 7.89 7.07 0.07
Relative organ weights (% of CW)
Liver 2.17 2.3 2.23 2.46 1.95 2.41 0.07
Kidney 0.51 0.97 1.0 0.98 0.83 0.96 0.04
Lung 0.54 0.74 0.66 0.74 0.73 0.73 0.02
Heart 0.54 0.57 0.47 0.53 0.42 0.50 0.01
Spleen 0.12 0.11 0.11 0.23 0.07 0.11 0.12
Gizzard 2.72 3.30 2.39 2.80 2.60 2.51 0.72
phase, feed intake was highest (p<0.05) for broilers on 5% increased in broilers fed 5% WC with or without VO
WC diet while other treatments had similar intake. Body while birds fed 7.5%WC diet had the least (p<0.05)
weight gain was similar across the dietary groups with the consumption. Body Weight Gain (BWG) and Feed
exception of broilers fed 7.5% WC based diets. Feed/gain Conversion Ratio (FCR) were significantly better
ratio was significantly (p<0.05) better for birds fed on the (P<0.05) on birds fed the control diet compared to those
control diet, 5% WC and 5% WC+VO diets compared to fed WC based diets without VO. The increase in feed
the other dietary groups however, broilers fed on 7.5% consumption for birds fed 5%WC did not really translate
WC had the worst feed conversion ratio. to higher weight gain. However, the slight improvement in
During the finisher phase, birds fed the control diet weight gain observed with the addition of VO is a
significantly (p<0.05) gave the highest BWG. Broilers on reflection of the positive attributes of vegetable oil in
5% WC with or without VO had the highest (p<0.05) feed poultry diets. Vegetable oil increases energy density,
consumption while the least intake was recorded for birds reduces dustiness and increase vitamin A concentration
fed 7.5% WC diet. The control diet exhibited the best-feed in diets [7, 9].
conversion ratio. Charcoal supplementation was reported to induce a
Considering the overall feeding period (combined small reduction in feed intake, egg production and feed
starter/finisher phases), feed intake was significantly conversion ratio [4]. The reduction in feed intake was
574
World J. Agric. Sci., 3 (5): 572-575, 2007
Table 4: Effect of dietary wood charcoal and supplemental vegetable oil on hematology of broilers
Diets
----------------------------------------------------------------------------------------------------------------------------------------
Variables 1 2 3 4 5 6 SEM
Packed cell volume (%) 29.00 26.50 25.50 24.50 26.00 25.00 0.24
Haemoglobin (gm %) 9.67 8.83 8.50 8.17 8.60 8.33 0.124
Red blood cell x106 4.83 4.42 4.25 4.05 4.30 4.15 0.58
White blood cell x103 8.83 9.03 9.95 9.60 6.23 6.35 0.57
Mean cell volume 59.90 60.00 60.00 60.60 60.50 60.40 0.58
Mean cell Haemoglobin 3.33 3.33 3.33 3.33 3.31 3.33 0.003
Mean cellHaemoglobin
concentrations 199.90 199.90 200.00 201.80 200.00 201.20 1.89
attributed to a higher bulk density of charcoal which was Majewska and Zaborowski, [5] Majewska, et al. [6]. So,
why VO was included in diets 5 and 6 to reduce bulkiness using WC in broiler diets is not recommended.
and dustiness. The blackening of the feed by the charcoal
might cause a degree of unpalatability [3]. This might REFERENCES
account for the significant reduction in intake for broilers
on 7.5% WC. Previous studies [5, 6] opined that the use 1. AOAC. 1990. The official methods of analysis.
of charcoal had a beneficial effect on the development of Association of Official Analytical Chemists, 13th Edn.
chickens and turkeys. For instance [5] observed that after Washinghton DC.
7 weeks of growth, birds which received supplemental 2. Davice, J.U. and S.M. Lewis, 1991. Practical
charcoal were about 1-6.5% heavier, had a 5.9% better haematology 8th edition. Longman Ltd London,
feed conversion efficiency and a 1.6% better survival rate pp: 22-48.
than the control group without wood charcoal. Similarly, 3. Jindal, N., S.K. Mahipal and N.K. Mahajan,
Majewska et al. [6] reported that turkeys given charcoal 1994. Toxicity of aflatoxin B3 in broiler chicks and
supplemental feeds were 5.9% heavier and had a 6.5% its reduction by activated charcoal, Res. Vet. Sci.,
better feed conversion ratio than the control birds. 56: 37-40.
Survival in the groups that received charcoal was 99% as 4. Kutlu, H.R., I. Unsal and M. Gorgulu, 2001. Effect of
compared to the 87.3% in the control group. providing dietary wood (oak) charcoal to broiler
The carcass yield, cut-up parts and organ weights of chicks and laying hens. Anim. Feed Sci. Tech.,
broilers fed WC and supplemental vegetable oil diets are 90: 213-226.
shown in Table 3 while the hematological indices are 5. Majewska, T. and M. Zaborowski, 2003. Charcoal in
indicated in Table 4. Broiler chickens fed 7.5%WC had the the nutrition of broiler chickens. Medycyna
least percentage carcass yield and abdominal fat among Weterynaryjina, 59: 81-83.
the dietary groups. Broiler cut-up parts and hematological 6. Majewska, T., D. Pyrek and A. Faruga, 2002. A note
parameters did not exhibit any major discernible response on the effect of charcoal supplementation on the
with the use of WC or supplemental VO in their diets. performance of Big 6 heavy tom turkeys. J. Anim.
However, the lung, heart and gizzard showed slight Feed Sci., 11: 135-141.
(p>0.05) changes among the dietary groups. These 7. Odunsi, A.A. and A.A. Onifade, 1998. Effect of zinc
showed that wood charcoal used in this study had no bacitracin supplementation of broiler chick diets
major physiological effects on tissue or organ containing a low or high vegetable oil concentration
development and functions. However a positive in the tropics. Trop. Vet., 16: 51-57.
development is the reduction in the abdominal fat 8. Steel, R.G.D. and J.H. Torrie, 1980. Principles and
deposition in broilers fed WC based diets relative to the procedures of statistics. A biometrical approach. 2nd
control group. edition McGraw Hill Books Co., New York, USA
This pilot study reported here demonstrated that the 9. Zollitscha, W., W. Knausa, A. Aichinegera and F.
wood charcoal incorporated into broiler chicken diet did Lettnera, 1997. Effects of different dietary fat sources
adversely affect broiler performance during the entire on performance and carcass characteristics of
feeding period as opposed to reports by Kutlu et al. [4] broilers. Anim. Feed. Sci. Technol., 66: 283-287.
575
Majewska T., Pyrek D., Faruga A.
Reference:
Poultry
Science
Vol
88
(Suppl
1)
,
p.
49.
2009
USDA ARS
Release of Inorganic Nitrogen and Phosphorus from
Poultry Litter Amended with Acidified Biochar
S.A. Doydora1, M.L. Cabrera1, K.C. Das2, J.W. Gaskin2, L.S. Sonon3, W. Miller1, and C. Steiner2
1Department of Crop and Soil Sciences, University of Georgia, Athens, GA 30602
2Department of Biological and Agricultural Engineering, University of Georgia, Athens, GA 30602
3Soil, Plant and Water Laboratory, 2400 College Station Road, Athens, GA 30602
sdoydora@uga.edu
Introduction
Georgia generates an estimated average of two million Mg poultry
litter (PL) annually. While this material is used as a fertilizer, its nitrogen
(N) value decreases as a result of ammonia (NH3) volatilization, which
may lead to losses of up to 60% of the applied N (Cabrera et al., 1993;
Cabrera and Chiang, 1994). One possible way of minimizing NH3
volatilization from PL is by mixing it with biochar (or char), a by-product
from bio-fuel production. When acidified, biochar may reduce NH3
volatilization from PL. This study aimed to 1) evaluate the effect of
acidified biochar on NH3 volatilization, 2) examine its effect on CO2
evolution and 3) determine its influence on the release of inorganic N
and P from surface-applied or incorporated PL.
Accession number;03A0266617
Title;Effects of feeding fowls with rice hull charcoal on the egg-laying performance and
the odor of chicken droppings.
Author;SAITO KATSUMI(Aomori Prefect. Livest. Exp. Stn., JPN)
KUZUMAKI TAKEFUMI(Kitasato Univ.) HOSOKAWA YOSHIHARU(Kitasato Univ.)
Journal Title;Tohoku Agricultural Research
Journal Code:F0596B
ISSN:0388-6727
VOL.;NO.55;PAGE.141-142(2002)
Figure&Table&Reference;TBL.2, REF.3
Pub. Country;Japan
Language;Japanese
Reasons for Pyrolysis of Poultry
Litter
• Traditionally, poultry litter is disposed by land
application and used as cattle feed
• Disposal of poultry litter in the U.S. poultry
industry is becoming a major problem because
of :
– Excess nutrient in the soil due to land application
– Contamination of drinking water
– Eutrophication of surface waters
– Ammonia emission from poultry houses
– Soil acidification through nitrification and leaching
– Biosecurity concerns
Pyrolysis conditions
• Feedstock---air-dried poultry litter
• Temperature---450 to 500 oC
• Residence time--- 2 to 5 s
• Fluidizing medium--- nitrogen or producer
gas
• Feed rate --- 200 g/h
Bench-Scale pyrolysis reactor
system
Bio-oil derived from Broiler litter
Poultry litter biooil
Pyrolysis Char of Broiler Litter
Bio-oil properties
Sample C H O N S (%) Moit pH Ash HHV
(%) (%) (%) (%) (%) (%) (MJ/kg
Chicken 55.25 6.54 37.58 <0.5 <0.05 5.3 2.7 <0.08 22.64
bedding
Flock-1 63.24 7.22 23.89 5.05 0.46 4.6 6.1 <0.09 28.25
litter
Flock-2 64.06 8.14 22.27 4.94 0.41 4.6 6.3 <0.09 28.0
litter
Broiler 62.84 8.31 20.72 7.23 <0.9 4.0 6.3 0.17 29.57
litter
Starter 64.90 8.44 20.31 5.60 0.4 3.7 4.2 0.10 29.76
turkey
litter
2500
2000
1500
Viscosity (cP)
Neat Biooil
MeOH + Biooil
EtOH + Biooil
1000
Ace + Biooil
500
0
0 10 20 30 40 50 60
Time (days)
Potential Applications of bio-oil
SYNTHESIS GAS OPTIONS
Cat: Ni, Fe, HYDROGEN
Cu-Zn
Cat: Cu-Zn, ETHANOL,
Bio-
Bio-oil Cu-Co MIXED ALCOHOLS
Cat: H3PO4,
Cr2O3 OLEFINS
FEED PREP
LPG
Cat: Fe
NAPHTHA
GASIFICATION Cat: Ni SYNGAS FTL UPGRADING
KEROSINE/DIESEL
Cat: Co/K LUBES
WAXES
Cat: Cu-ZnO MeOH Cat: Zeolite GASOLINE
CLEANUP
CaCN AMMONIA
Cofiring/Reburn CHP
Biomass Pyrolysis (liquefaction)
Bio-Oil FromBio-oil Uses
Dolomite
Raw
Compress LBG LBG ESP and Oil Product
ed Reheat Compression Coalescing
Air Burner System
Excess LBG
to Feed
Startup
Dryer
LPG
Thermochemical conversion of biomass
to biofuels
Foster A. Agblevor,
Biological Systems Engineering
Virginia Tech, Blacksburg, VA.
Email: fagblevo@vt.edu
Constituents
HO OCH3 O
O O OH
OCH3OCH3 O
O HO OH
O
OCH3
OH OCH3
O O
HO
HO OH O OH
O O HO
HO O OH
O
OH OH OH
OH OH O
OCH3 H3CO HO
OCH3 O O HO
Lignin: 15-25% O
OCH3OCH3
OCH3
HO
O
HO
OH
O
OH
OH O
O
OH
HO
OH
O
OH O OH
O HO O HO
Complex aromatic structure O
O
OH OH
O
OH OH
O OH O
OH OH
O
HO OH OH O OH O
Hemicellulose: 23-32%
O
HO OH O HO OH O
O O
O HO O HO
O OH O OH
OH OH
O OH OH
O
OH O OH O
HO HO
OH O HO OH O
sugar OH O
O HO
OH Solid
OH OH
O
OH O
HO
OH O HO
O
OH
OH O
Cellulose: 38-50% OH
Chicken 55.25 6.54 37.58 <0.5 <0.05 5.3 2.7 <0.08 22.64
bedding
Flock-1 63.24 7.22 23.89 5.05 0.46 4.6 6.1 <0.09 28.25
litter
Flock-2 64.06 8.14 22.27 4.94 0.41 4.6 6.3 <0.09 28.0
litter
Broiler 62.84 8.31 20.72 7.23 <0.9 4.0 6.3 0.17 29.57
litter
Starter 64.90 8.44 20.31 5.60 0.4 3.7 4.2 0.10 29.76
turkey
litter
2500
2000
1500
Viscosity (cP)
Neat Biooil
MeOH + Biooil
EtOH + Biooil
1000
Ace + Biooil
500
0
0 10 20 30 40 50 60
Time (days)
Potential Applications of bio-oil
SYNTHESIS GAS OPTIONS
Cat: Ni, Fe, HYDROGEN
Cu-Zn
Cat: Cu-Zn, ETHANOL,
Bio-
Bio-oil Cu-Co MIXED ALCOHOLS
Cat: H3PO4,
Cr2O3 OLEFINS
FEED PREP
LPG
Cat: Fe
NAPHTHA
GASIFICATION Cat: Ni SYNGAS FTL UPGRADING
KEROSINE/DIESEL
Cat: Co/K LUBES
WAXES
Cat: Cu-ZnO MeOH Cat: Zeolite GASOLINE
CLEANUP
CaCN AMMONIA
Cofiring/Reburn CHP
Biomass Pyrolysis (liquefaction)
Bio-Oil FromBio-oil Uses
Dolomite
Raw
Compress LBG LBG ESP and Oil Product
ed Reheat Compression Coalescing
Air Burner System
Excess LBG
to Feed
Startup
Dryer
LPG
Transportable Pyrolysis Unit
Rockingham County Cooperator
• A pilot pyrolysis unit will be demonstrated
on the property of our cooperator, Mr.
Oren Heatwole.
• The unit will be transportable from farm to
farm, but most of the initial research will be
done on-site.
• Poultry litter from a neighboring farm will
be used as the feedstock for the pilot
project.
Modified Furnace for Using Bio-
Oil
ADI Stirling Engine System
Runs on Heat
2. Furnace
3. Thermocouple
5. Heat Exchanger
6. Hopper
7. Sample Feeder
8. Computer
9. Heating Tape
10. Cyclone
11. Reservoir
12. Condenser
15. Filter
FCP oil
50 oC
Viscosity [ Pa.sec ]
25 14 60 oC
10
20 12
8
Viscosity [ Pa.sec ]
10
6 15
8
4
10
6
2
5
4
0
0 100 200 300 400 500 0
0 20 40 60 80 100 120 2
-1
Shear rate [ min ]
Shear rate [ min-1 ] 0
0 100 200 300 400 500
-1
Shear rate [ min ]
Viscosity of biooil ; Turkey Litter, 450 ℃, 500 ℃,
550 ℃
14
50 oC
60 oC
12
10
Viscosity [ Pa.s]
14
50 oC
8
12 60 oC
Viscosity [ Pa.sec ]
10
70
4
8 o
50 C
o
60 60 C
2
6
Viscosity [ Pa.sec ]
50
0
4
0 100 200 300 400 500
-1 40
Shear rate [ min ] 2
30
0
0 100 200 300 400 500
20
-1
Shear rate [ min ]
10
0
0 20 40 60 80 100 120
-1
Shear rate [ min ]
Comparison of HHV of biooil and
litter samples
Raw sample Biooil HHV
Sample
HHV (Btu/lb) (Btu/lb)
Chicken 7,792 8,408
Bedding
Flock 1 6,514 11,829
Abstract
The influence of charcoal on biotic processes in soils remains poorly understood. Charcoal is a natural product of wildfires that burned on a
historic return interval of w100 years in Scots pine (Pinus sylvestris L.) forests of northern Sweden. Fire suppression and changes in forest
stand management have resulted in a lack of charcoal production in these ecosystems. It is thought that charcoal may alter N mineralization
and nitrification rates, however, previous studies have not been conclusive. Replicated field studies were conducted at three late-succession
field sites in northern Sweden and supporting laboratory incubations were conducted using soil humus collected from these sites. We used
activated carbon (AC), as a surrogate for natural-occurring fire-produced charcoal. Two rates of AC (0 and 2000 kg haK1), and glycine (0 and
100 kg N as glycine haK1) were applied in factorial combination to field microplots in a randomized complete block pattern. Net nitrification,
N mineralization, and free phenol concentrations were measured using ionic and non-ionic resin capsules, respectively. These same
treatments and also two rates of birch leaf litter (0 and 1000 kg haK1) were applied in a laboratory incubation and soils from this incubation
were extracted with KCl and analyzed for NHC 4 and NO3 . Nitrification rates increased with AC amendments in laboratory incubations, but
K
this was not supported by field studies. Ammonification rates, as measured by NHC 4 accumulation on ionic resins, were increased
considerably by glycine applications, but some NHC 4 was apparently lost to surface sorption to the AC. Phenolic accumulation on non-ionic
resin capsules was significantly reduced by AC amendments. We conclude that charcoal exhibits important characteristics that affect
regulating steps in the transformation and cycling of N.
q 2004 Elsevier Ltd. All rights reserved.
Keywords: Activated carbon; Charcoal; Boreal forest; Birch litter; Fire; Nitrogen transformations; Nitrification; Phenolic compounds
concentrations of available ammonium (NHC 4 ) present after short-term studies, we only observed a nitrification response
fire are produced chemically by soil heating during fire to AC at a relatively high and potentially unrealistic
and also by increased microbial activity following fire application rate and the work was performed at only one
(Choromanska and DeLuca, 2002). A pulse of available field site. Thus it is not clear if nitrification rates would be
nitrate (NOK 3 ) occurs within a year after fire and since NO3
K
significantly altered by AC additions to forest soils at lower,
is not produced directly by heating this is commonly naturally-occurring quantities. Furthermore, it was not clear
attributed to increased nitrification in excess of ammonium whether the presence of birch (Betula pubescence Ehrh)
(Wan et al., 2001). The long-term effect of fire on N litter (as is common in early succession) would also
mineralization rates is not clear. Although fire appears to influence nitrification rates as has been found in studies
reduce stocks of mineralizable N (Monleon et al., 1997; involving aspen litter (Ste-Marie and Paré, 1999).
Kaye and Hart, 1998; DeLuca and Zouhar, 2000) through We hypothesized that charcoal would enhance rates of
volatilization and fuel combustion, other changes in nitrification in boreal forest soils. We used AC, as a
N transformation are normally attributed to changes in surrogate for natural-occurring fire-produced charcoal with
the composition of plant communities and soil biota (Hart the intention of investigating the effect of AC on net N
et al., 2004). mineralization and nitrification rates in Scots pine forests.
Many of the dwarf shrubs commonly found in late We also attempted to determine whether these effects were
successional Swedish boreal forests are known to produce related to AC adsorption of free phenolic compounds from
large quantities of phenolic compounds (Gallet and the soil.
Lebreton, 1995; Nilsson et al., 1998) that may directly
influence nutrient turnover and microbial activity (Wardle
et al., 1997). Polyphenolic compounds can affect N cycling 2. Materials and methods
by stimulating microbial soil processes. Microorganisms
use polyphenols as a C source and with increased need of N 2.1. Site descriptions
this promotes N immobilization. Formation of protein–
tannin complexes by polyphenolic compounds may also Studies were conducted on a total of three forest stands in
impede mineralization and help to build up thick mor layers northern Sweden. All sites are situated in forests reserves
of recalcitrant organic material (Northup et al., 1995). within the northern boreal zone and consist of late-
The influence of charcoal on maintaining N availability successional Pinus sylvestris L. dominated forest of
has been addressed by Wardle et al. (1998) and DeLuca ericaceous-cladina type on sandy glacial soils (Ahti et al.,
et al. (2002). Fire-produced charcoal has a porous structure 1968), classified as either Typic or Entic Haplocryods.
and sorptive surfaces which are shown to have the capacity Pleurozium schreberi (Bird.) Mitt. and Cladina spp are the
to adsorb significant amounts of polyphenolic compounds dominant bottom-layer moss and lichen taxa and the field-
(Zackrisson et al., 1996) and this effect is similar to layer mainly consists of the ericaceous shrubs Empetrum
commercially-produced activated carbon (AC). Such hermaphroditum Hagerup and Vaccinium vitis-idaea L.
adsorption may result in deactivating the phenols through Composite samples of the forest duff layer (Oe/Oa horizons)
chemical condensation of the phenols (Piccolo et al., 1999) were collected at each site and analyzed for pH, total C and
preventing toxic allelopatic effects and an increase in total N. General soil and site characteristics are presented in
microbial activity due to accumulation of dissolved C as a Table 1.
food source and thereby increase mineralization. Charcoal
has been shown to harbour and support specific or unique 2.2. Laboratory study
microbial communities (Pietikäinen et al., 2000), although
little is known on the functional differences of these special A laboratory incubation experiment was conducted to
communities. The porous structure of charcoal has also been assess the influence of charcoal and litter on net N
suggested to shelter microbial organisms from soil faunal mineralization rates and nitrification rates in boreal soils
predators (Wardle et al., 1998). under controlled conditions. Samples from humus layer
Studies in our laboratory suggested that nitrification rates were collected from the three P. sylvestris dominated sites.
are directly influenced by the addition of AC, used as a The humus was sieved (!5 mm) to remove coarse roots,
surrogate for soil charcoal (DeLuca et al., 2002). In these mixed thoroughly and then air dried (20 8C) for 3 days.
Table 1
General soil and site characteristics for each site
Site Location pH (GSE) Humus C (%) Humus N (%) Soil C (%) Soil N (%)
Reivo 65846 0 N, 19806 0 E 4.06 (0.03) 45.85 1.05 3.3 0.09
Vaksliden 65842 0 N, 18845 0 E 4.14 (0.02) 44.98 1.00 1.2 0.04
Strömforsheden 65808 0 N, 18853 0 E 4.06 (0.06) 48.31 1.20 2.3 0.10
L.M. Berglund et al. / Soil Biology & Biochemistry 36 (2004) 2067–2073 2069
Then 10 g of humus (dry weight) was placed in 300 ml microplot. Free phenols were monitored by placing one
(9 cm diameter) polyethylene jars. The humus was then polyester capsule (Unibest, Bozeman, MT) filled with
amended with one of the following treatments: 1) 0 or approximately 1 g dwt (about 1100 m2 of surface area) of
100 kg N haK1 as glycine (Sigma Scientific) as an organic XAD-7 resin (Rohm and Hass Inc., Philadelphia, PA), near
N source; 2) 0 or 2000 kg AC haK1; 3) 0, or 1200 kg birch the ionic resin capsule at the interface of the O horizon and
litter haK1. This combination of treatments resulted in a mineral soil in each microplot. In total, 120 ionic and 120
2!2!2 factorial experiment of 6 replicates for each of the non-ionic resin capsules were used. In order to locate the
three sites, in total 144 jars. Treatments were applied by buried capsules, a thin nylon-line had been attached to each
mixing each component thoroughly with humus and then resin capsule and the line was then attached to a marker
placing the combined material into the polyethylene jar. The above ground when the capsule was buried. The resin
AC was applied as 1.28 g of activated C (representing capsules were allowed to remain in the field for 2.5 months
2000 kg haK1) added to each pot and the glycine was from 11–18 June to 23 September, 2002. All capsules were
applied to the humus as a solution of 340 mg glycine then removed from each plot, and stored at K20 8C until
(535 kg glycine haK1 representing 100 kg N haK1) mixed analysis.
with distilled water. Dried birch leaf litter (Betula
pubescence Ehrh) was fragmented (4–5 mm) and 800 mg 2.4. Chemical analyses
was mixed into the humus. All the samples were adjusted to
a moisture content of 60% of maximum water holding Forest O horizon samples were analyzed for total C and
capacity (MWHC) and this was checked, and amended once N by dry combustion using an elemental analyzer
a week during the experiment. The jars were covered with (PerkinElmer 2400 CHN, Norwalk, Connecticut, USA).
plastic lids with air-holes and incubated for 8 weeks at 13 8C Soil pH was determined in distilled water using a 2:1
and 70% relative humidity. At the end of the experiment soil solution to soil ratio.
samples were dried in 70 8C for 3 days and stored until Soil mineral N in 2.5 g of the incubated soil samples was
analysis. extracted with 25 ml 2 M KCl on a shaker for 1 h, followed by
filtration through Whatman No 42 filters. The extractable
2.3. Field study NHC 4 and NO3 were then analyzed by using a segmented flow
K
microplots from 0 to 10 cm depth within the forest floor as a reported as mg NH4 –N or NO3 –N capsuleK1. Non-ionic
C K
solution (glycine) or suspension (AC) by using a 50 ml resin capsules were analyzed for polyphenols following a
syringe with a 80 mm long, 2.10 mm wide steel needle. This sequential extraction with water followed by 50% aqueous
approach allowed for rapid incorporation of the AC methanol (Morse et al., 2000). Each capsule was placed in a
throughout the microplot with minimal disturbance to the polypropylene centrifuge tube with 30 ml of distilled water,
forest floor. The AC treatment was applied as 200 ml of the shaken for 30 min, and the aqueous fraction was decanted
40 g AC lK1 suspension. The glycine treatment was applied into a glass vial and stored at K20 8C until analysis. The
as 100 ml of glycine solution (21.4 g glycine lK1). Distilled resin capsule was then immersed in 10 ml of 50% aqueous
water was added at the same rate as in the glycine and AC methanol and shaken for 30 min. Extracts were decanted
treatment. into clean glass vials and this process was repeated for a
Net N mineralization and nitrification were monitored second and third time to create a total extraction volume of
in situ at these sites by using ionic resin capsules and free 30 ml. The methanol extracts were stored at K20 8C until
polyphenols were monitored in situ by using non-ionic analysis for polyphenolic compounds. Polyphenol analysis
carbonaceous resin capsules (DeLuca et al., 2002). This was performed by using the Prussian blue technique (Stern
approach allows NOK 3 , NH4
C
and polyphenols to be et al., 1996) measured against catechin standards at 720 nm.
assessed over a specific period rather than taking a single
point-in-time sample or using disruptive net N mineraliza- 2.5. Statistical analysis
tion techniques. One polyester capsules containing 10 ml
(approximately 1 g dwt) of mixed bed ionic resins (PST-2, The N and polyphenol data were analyzed using
Unibest, Bozeman, MT) were placed at the bottom of the Oa ANOVA. All data were analyzed for normality and
horizon or near the interface with the mineral soil in each homogeneity of variance. Data found to violate assumptions
2070 L.M. Berglund et al. / Soil Biology & Biochemistry 36 (2004) 2067–2073
Table 2
Average pH in laboratory incubation from all three boreal forest sites,
incubated for 8 weeks
Treatment pH
0 3.62
CC 3.88
CL 3.85
CG 5.59*
CCCL 4.06
CLCG 5.62*
CCCG 5.75*
CCCGCL 5.73*
treatment, where glycine was added alone (Fig. 1). The accumulation on ionic resin capsules in the field was small
amount of NOK (Fig. 4) and there were no significant differences in the
3 in the presence of AC and glycine was
almost double (5–6 mg NOK compared to 3 mg amount of accumulated NOK between treatments or
3 –N g soil
K1 3
Monleon, V.J., Cromack Jr.., K., Landsberg, J.D., 1997. Short- and long- Steijlen, I., Zackrisson, O., 1987. Long-term dynamics and successional
term effects of prescribed underburning on nitrogen availability in trends in a northern Swedish coniferous forest stand. Canadian Journal
ponderosa pine stands in central Oregon. Canadian Journal of Forest of Botany 65, 879–898.
Research 27, 369–378. Ste-Marie, C., Paré, D., 1999. Soil pH and N availability effects on net
Morse, C.C., Yevdokimov, I.V., DeLuca, T.H., 2000. In situ extraction and nitrification in the forest floors of a range of boreal forest stands. Soil
analysis of rhizosphere carbon of native and invasive plant species. Biology & Biochemistry 31, 1575–1589.
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Neary, D.G., Klopatek, C.C., DeBano, L.F., Ffolliott, P.F., 1999. Fire A new assay for quantifying brown algal phlorotannins and compari-
effects on belowground sustainability: a review and synthesis. Forest sons to previous methods. Journal of Chemical Ecology 22, 1273–1294.
Ecology and Management 122, 51–71. Tate, R.L., 1995. Soil Microbiology. Wiley, New York.
Nilsson, M.-C., Gallet, C., Wallstedt, A., 1998. Temporal variability of Wan, S., Hui, D., Luo, Y., 2001. Fire effects on nitrogen pools and
phenolics and batatasin III in Empetrum hemaphroditum leaves over an dynamics in terrestrial ecosystems: a meta-analysis. Ecological
eight year period: interpretation of ecological function. Oikos 81, 6–16.
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Wardle, D.A., Zackrisson, O., Hörnberg, G., Gallet, C., 1997. The influence
nitrogen release from pine litter. Nature 377, 227–229.
of island area on ecosystem properties. Science 277, 1296–1299.
Paavolainen, L., Kitunen, V., Smolander, A., 1998. Inhibition of
Wardle, D.A., Zackrisson, O., Nilsson, M.-C., 1998. The charcoal effect on
nitrification in forest soil by monoterpens. Plant and Soil 205, 147–157.
boreal forests: mechanisms and ecological consequences. Oecologia
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sequestration of organic carbon in soil by hydrophobic protection.
Naturwissenschaften 86, 496–499. White, C.S., 1994. Monoterpens- their effect on ecosystem nutrient cycling.
Pietikäinen, J., Kiikkilä, O., Fritze, H., 2000. Charcoal as a habitat for Journal of Chemical Ecology 20, 1381–1406.
microbes and its effect on the microbial community of the underlying Zackrisson, O., 1977. Influence of forest fires on the north Sweden boreal
humus. Oikos 89, 231–242. forest. Oikos 29, 22–32.
Stark, J.M., Hart, S.C., 1997. High rates of nitrification and nitrate turnover Zackrisson, O., Nilsson, M.-C., Wardle, D.A., 1996. Key ecological
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Biol Fertil Soils (2007) 43:303–311
DOI 10.1007/s00374-006-0106-5
ORIGINAL PAPER
Received: 26 July 2005 / Revised: 10 April 2006 / Accepted: 12 April 2006 / Published online: 3 June 2006
# Springer-Verlag 2006
Abstract We conducted laboratory and greenhouse experi- laboratory-generated charcoal and wildfire-produced char-
ments to determine whether charcoal derived from the coal. Furthermore, they suggest a need for a better
ponderosa pine/Douglas-fir ecosystem may influence soil understanding of how temperature and substrate influence
solution chemistry and growth of Koeleria macrantha, a the chemical properties of charcoal.
perennial grass that thrives after fire. In our first experi-
ment, we incubated forest soils with a factorial combination Keywords Charcoal . Soil solution chemistry .
of Douglas-fir wood charcoal generated at 350°C and Douglas-fir and ponderosa pine ecosystems
extracts of Arctostaphylos uva-ursi with and without the
addition of glycine as a labile N source. These results
showed that charcoal increased N mineralization and Introduction
nitrification when glycine was added, but reduced N
mineralization and nitrification without the addition of It is well-established that fire alters N cycling in the
glycine. Charcoal significantly reduced the solution con- ponderosa pine/Douglas-fir (Pinus ponderosa/Psuedotsuga
centration of soluble phenols from litter extracts, but may menziesii) ecosystem (Neary et al. 1999; Hart et al. 2005).
have contributed bioavailable C to the soil that resulted in Nitrogen availability has been shown to increase immedi-
N immobilization in the no-glycine trial. In our second ately after fire (Covington and Sackett 1990, 1992; DeLuca
experiment, we grew K. macrantha in soil amended with and Zouhar 2000) and may remain elevated on the scale of
charcoal made at 350°C from ponderosa pine and Douglas- months to years as a result of enhanced mineralization
fir bark. Growth of K. macrantha was significantly (Covington and Sackett 1990, 1992; Monleon et al. 1997;
diminished by both of these charcoal types relative to the Kaye and Hart 1998; Gundale et al. 2005). Numerous
control. In our third experiment, we grew K. macrantha in processes that increase N mineralization after fire have been
soil amended with six concentrations (0, 0.5, 1, 2, 5, and identified, including improved substrate quality (White
10%) of charcoal collected from a wildfire. The data 1991, 1994; Fernandez et al. 1997; Pietikainen et al.
showed increasing growth of K. macrantha with charcoal 2000a), death of roots and soil organisms resulting in a
addition, suggesting some fundamental differences between large labile organic N pool (DeBano et al. 1979; Dunn et al.
1979; Diaz-Ravina et al. 1996; Neary et al. 1999), and a
reduction in C to N ratios due to preferential loss of C
M. J. Gundale (*) : T. H. DeLuca
during combustion (Gundale et al. 2005). A potentially
Department of Ecosystem and Conservation Sciences
University of Montana, overlooked factor that may also enhance N cycling after fire
32 Campus Drive, is the addition of charcoal to soils.
Missoula, MT 59812, USA Several recent studies have shown that charcoal has the
e-mail: mjgundal@yahoo.com
potential to greatly enhance soil fertility. Amazonian forest
T. H. DeLuca soils amended centuries ago with charcoal and manure still
e-mail: tom.deluca@cfc.umt.edu maintain some of the highest biodiversity and productivity
304 Biol Fertil Soils (2007) 43:303–311
of any soils within the Amazon basin (Glaser et al. 2001, In our third experiment, our objective was to determine
2002; Mann 2002). In boreal forest soils, charcoal was whether charcoal generated during a wildfire would have
shown to enhance N cycling by ameliorating the inhibitory any effect on K. macrantha growth and to determine
effects of litter extracts from late-successional species, whether this relationship is dependent on soil charcoal
which in turn promotes growth of early-successional concentration. We hypothesized that wildfire charcoal will
species (Zackrisson et al. 1996; Wardle et al. 1998; DeLuca positively influence K. macrantha and that this effect will
et al. 2002; Berglund et al. 2004). Recently, DeLuca et al. increase as a function of soil charcoal concentration.
(2006) found that the addition of wildfire-formed charcoal Collectively, these three experiments address our central
to ponderosa pine forest soils increased nitrification rates. hypothesis that charcoal will alter solution chemistry by
Charcoal may enhance soil fertility through a variety of sorbing phenols and enhancing N cycling, which in turn
mechanisms. Increased N turnover may occur by charcoal will improve the growth of early successional species.
sorption of high C:N organic molecules from the soil
solution (Zackrisson et al. 1996; Wardle et al. 1998; Glaser
et al. 2002), resulting in reduced microbial N immobiliza- Materials and methods
tion and higher net mineralization and nitrification rates. In
addition, charcoal may remove specific groups of organic All three experiments utilized field-collected soil, which
molecules, including polyphenol or monoterpene com- was collected from the subsurface horizon (20–30 cm, Bw
pounds that are thought to inhibit nitrification (Rice and Horizon) of a forest soil associated with low elevation
Pancholy 1972; Zackrisson et al. 1996; DeLuca et al. 2002; (1,100 m) ponderosa pine/Douglas-fir vegetation in western
Berglund et al. 2004). Sorption of organic molecules, along Montana, USA. The soil is a sandy-skeletal, mixed, frigid
with the gradual breakdown of charcoal, may initiate Typic Dystrustepts. This ecosystem is characterized by low
humus formation and, thus, enhance long-term soil fertility annual rainfall (<350 mm annually) with approximately
(Glaser et al. 2002). Charcoal may also enhance soil 50% falling as snow during the winter months. Soil was
fertility by creating habitat for microbes within its porous collected during the month of September, returned to the
structure (Pietikainen et al. 2000b). lab, upon which they were sieved (4 mm) and homoge-
Despite these potential roles that charcoal may have in nized. We then added one part sand to three parts field
increasing soil fertility, its ecological role in forest ecosys- moist soil (by mass) to decrease fertility and increase
tems, such as ponderosa pine/Douglas-fir, has received little porosity and gas exchange, such that nitrification would not
attention. We conducted three separate experiments using be limited by low O2 availability. The sand fraction was
low-temperature charcoal to investigate whether charcoal purchased as filter grade silica sand (for pool filters) and
influences soil solution chemistry and growth of an early was washed with 1 M HCl, followed by distilled water,
successional species. In our first experiment, our objective before being homogenized with field collected soil. This
was to determine whether charcoal had an influence on soil sand-amended soil had a pH of 6.8, electrical conductance
solution chemistry after addition of the extracts of a late of 91.2 μS m−1, and had a textural distribution of 71%
successional species, Arctostapholos uvi-ursi, via surface sand, 21% silt, and 8% clay.
adsorption of phenolic compounds. We hypothesized that All experiments also included the addition of either
charcoal added to a ponderosa pine forest soil will laboratory-generated charcoal from Douglas-fir and ponder-
effectively sorb the phenol fraction in litter extracts, which osa pine or charcoal collected in the field after a wildfire.
would correspond with enhanced N cycling. Laboratory charcoal was generated by burying wood or bark
In our second experiment, our objective was to compare from these species in silica sand and heating at 350°C for 2 h.
the influence of charcoal made from the bark of two Charcoal was then ground and sieved as specified for each
species, ponderosa pine and Douglas-fir, on growth of experiment. Various physical and chemical properties of these
Koeleria macrantha, a perennial grass species that thrives charcoals were measured (Table 1). Charcoal pH was
after fire disturbance in western Montana ponderosa pine/ measured from a 4:1 slurry of deionized water to charcoal.
Douglas-fir forests. Bark charring during low-intensity Electrical conductance (EC) was measured from charcoal
wildfire is a potentially significant source of charcoal in paste (2:1 distilled water and charcoal). Cation exchange
this system. Charred bark may gradually slough from trees capacity (CEC) was estimated on charcoal samples via NHþ 4
after fire and become incorporated in the soils surrounding replacement where 1 g of charcoal was rinsed twice with
trees. It is recognized that ponderosa pine is a more fire- 25 ml of 1 M ammonium acetate (pH 7) to saturate exchange
adapted species than Douglas-fir; thus, an intriguing sites. Excess saturating solution was removed from charcoal
hypothesis is that charred bark of the more fire-adapted samples with three consecutive washes with 25 ml of 95%
species will have a stronger positive effect on N cycling ethyl alcohol. Sorbed NHþ 4 was then extracted with 25 ml of
processes and plant growth. 2 M KCl and analyzed on a segmented flow analyzer (Auto
Biol Fertil Soils (2007) 43:303–311 305
Table 1 Chemical properties of four charcoal types (df Douglas-fir, extract was 267.5 mg/l. Extract treatments received 25 ml
pp ponderosa pine, wildfire wildfire collected) used in the laboratory of this extract. No-extract treatments received an equivalent
and greenhouse experiments
volume of deionized water. Soils were homogenized
df Wood df Bark pp Bark Wildfire following this addition. This addition brought the soil in
each mason jar to a water content of approximately 60%
pH 4.15 4.18 4.81 5.74
WHC. Mason jars were incubated in the dark for 14 days
EC (μS g−1) 20.5 24.2 111.6 141.5
CEC (cmolc kg−1) 20.66 19.42 34.48 29.35
after which a portion of the soil was extracted and analyzed.
Density (g cm−3) 0.30 0.08 0.21 0.29 This entire experiment was repeated exactly as described
Total C (%) 72.9 72.4 71.5 82.3 above but with glycine added to all mason jars as a source of
Soluble phenols (μg g−1) 34.9 30.7 43.4 48.2 highly labile organic N to stimulate a more marked N
Total phenols (μg g−1) 441.7 148.1 810.4 393.8 response. Glycine, a simple amino acid that is readily
−1
PO3
4 (μg g ) 0.94 0.84 2.46 0.95 mineralized to NHþ
−1 4 , was added to each mason jar at a rate
NH4 (μg g )
þ
7.12 9.0 5.6 38.3
−1 of 75 mg/jar (250 mg/kg of soil). These two experiments will
NO3 (μg g ) 0.12 0.3 0.0 4.4
hereafter be referred to as the glycine and no-glycine trials.
Analyzer III, Bran Luebbe, Chicago, IL) using the Berthelot Experiment 2: effects of bark charcoal on plant growth
reaction (Willis et al. 1993). Charcoal density was measured
by measuring dry mass of intact charcoal pieces and This greenhouse experiment consisted of three treatments
measuring volume displacement in deionized water. Total (Douglas-fir charcoal, ponderosa pine charcoal, and a
C was measured via dry combustion on a Fissions Elemental control) using the sand-amended soil described above to
Analyzer (Milano, Italy). Soluble and total phenols were evaluate the influence of charcoal source on K. macrantha.
measured by extracting 1 g of ground charcoal in 25 ml of Each treatment consisted of 20 replicate pots where each
deionized water and 50% methanol, respectively, and were pot received 1.5 kg of soil, and charcoal treatments received
analyzed using the Prussian Blue Method (Stern et al. 1996). a 2% (by mass) charcoal amendment. One percent of this
Extractable NHþ 4 and NO3 (Mulvaney 1996) were extracted
charcoal was homogenized into the soil, while the other 1%
by shaking 1 g of charcoal for 30 min in 25 ml of 2 M KCl, was evenly distributed on the soil surface. We made
and then filtering through Whatman #2 filters. The extracts charcoal from Douglas-fir and ponderosa pine in the
were analyzed for NHþ 4 –N using the Berthelot reaction laboratory by burying bark of each species in silica sand
(Willis et al. 1993) and NO 3 –N by the cadmium reduction and heating to 350°C in a muffle furnace for 2 h. Charcoal
method (Willis and Gentry 1987) on a segmented flow was ground and sieved (<1 mm) using a Wiley mill.
analyzer (Auto Analyzer III). Soluble PO34 was extracted by Organic horizons (Oi, Oe, and Oa) were added to the surface
placing 1 g of charcoal in 25 ml of 0.01 M CaCl2 for 30 min. of each pot to add an additional and substantial mineraliz-
Extracts were filtered through Whatman #42 filter paper and able pool of plant essential nutrients, as well as to provide a
then analyzed on a segmented flow analyzer using the source of bioavailable organic C that may influence soil
molybdate method as described by Kuo (1996). nutrient transformations. This organic material was ran-
domly collected (as described in Gundale et al. 2005) from
Experiment 1: charcoal sorption potential a ponderosa pine/Douglas-fir forest that had not been
exposed to fire for approximately 80 years and originated
We conducted a laboratory incubation study using the soil from numerous species, including understory and overstory
described above, where Douglas-fir charcoal and extract of species, but appeared to be primarily composed of
Arctostaphylos uva-ursi were added in a factorial combi- undecomposed ponderosa pine and Douglas-fir litter. The
nation yielding four treatments (Charcoal/Extract, Charcoal/ organic material was homogenized and 100 g was added to
No extract, No Charcoal/Extract, and No Charcoal/No the surface of each pot. A mixed bed ionic resin capsule
extract). Each treatment was replicated five times and (Unibest, Bozeman, MT) was placed in the center of each
consisted of 300 g of soil and placed into mason jars. The pot to sorb nutrients throughout the duration of the
treatments receiving charcoal addition received a 2% experiment.
charcoal amendment (20 g/kg). Charcoal was generated in K. macrantha was grown in these pots between October
a muffle furnace by submerging Douglas-fir wood in sand 2004 and March 2005 under ambient light conditions. An
and heating it at 350°C for 2 h. Charcoal was ground and average greenhouse temperature of 21°C was maintained. K.
sieved through a 4.75-mm sieve. A. uva-ursi extract was macrantha seeds (Western Native Seeds, Coaldale, CO)
made by extracting 100 g of A. uva-ursi leaves in 1 l of were germinated in a separate soil medium, and a single
deionized water for 24 h and filtering this extract through seedling was transplanted into each pot. Pots were watered
Whatman #42 filters. The total phenol concentration of this 3 days a week throughout the duration of the experiment. At
306 Biol Fertil Soils (2007) 43:303–311
the end of the experiment, resin capsules were recovered, Statistical analyses
and soil was rinsed from roots. Plants were oven-dried at 65°C,
and above- and belowground masses were measured. Data in experiment 1 meeting assumptions of normality and
homoscedasticity were analyzed using two-factor analysis
Experiment 3: effect of wildfire charcoal on plant growth of variance (ANOVA), where extract and charcoal were
entered as fixed factors under the general linear model.
Charcoal collected from a wildfire site was added to the soil Variables not meeting these assumptions were analyzed
described above at a rate of 0, 0.5, 1, 2, 5, and 10%, and using a Kruskal–Wallis test (K–W test). This analysis tests
placed in greenhouse pots seeded with K. macrantha to for differences among treatments but does not evaluate the
determine whether an increase in soil charcoal content has significance of individual factors or interactions between
any influence on the growth of K. macrantha. Each factors.
treatment (n=10) was established by adding 1.0 kg of Data in experiments 2 and 3 were analyzed using one-
charcoal-amended soil per pot. The charcoal used in this factor ANOVA followed by the Student–Newman–Keuls
experiment differed from both previous experiments because post hoc procedure. Different letters are used to display post
it was collected after a wildfire rather than generated in the hoc differences. Data not meeting assumption of normality
laboratory. Large particles (>5-cm diameter) of charcoal and homoscedasticity were compared using K–W tests,
were collected in the spring of 2004 from the Black which were not followed by post hoc procedures. All
Mountain Fire (August 2003), Missoula, MT, (DeLuca et analyses were conducted using SPSS 12.0 software.
al. 2006). It was impossible to decipher the species origin of
this charcoal, but it was likely primarily Douglas-fir and
ponderosa pine wood and bark char. The charcoal particles Results and discussion
were crushed, using a mallet, producing fragments ranging
from a diameter of 2 cm to microscopic. No attempt was Experiment 1: low temperature charcoal sorption potential
made to discriminate against any size class in an attempt to
simulate the range of charcoal particle sizes likely incorpo- Both charcoal and litter extract significantly influenced
rated into the soil under natural conditions. Organic horizon numerous soil chemical variables (Fig. 1). In both glycine
materials (50 g) were collected from a forest stand not and no-glycine trials, litter extract negatively influenced
exposed to fire for over 80 years and added to the surface of extractable NO 3 concentrations. The negative influence of
each pot as described earlier. All other experimental A. uva-ursi on extractable NO 3 reported here is consistent
conditions were run identically to experiment 2. with our previous studies in ponderosa pine forest soils
(DeLuca et al. 2006) and with studies that showed that litter
Laboratory analyses from late-successional boreal species, such as the ericaceous
shrub Empetrum hermaphroditum, diminishes net nitrifica-
At the end of experiment 1, 30 g of soil were extracted with tion (DeLuca et al. 2002; Berglund et al. 2004). Charcoal
2 M KCl and analyzed for NHþ 4 and NO3 as described
had an unexpected negative effect on NO 3 in the no-glycine
above. Amino N was measured on these same extracts trial. In contrast, the addition of charcoal increased NO 3
using the ninhydrin method (Moore 1968). Soluble phenols concentrations in the glycine trial. These results may be a
were extracted by shaking 30 g of soil for 1 h with 50 ml of function of the charcoal we used in this study, which was
deionized water followed by filtration. Sorbed phenols were generated at a low temperature (350°C). Charcoal contains a
extracted by shaking 30 g of soil with 50% methanol for significant concentration of bioavailable C, specifically
24 h followed by filtration. Phenols in these extracts were soluble phenols (Table 1) that may have caused net NO 3
measured using the Prussian blue method (Stern et al. immobilization (Schimel et al. 1996) in the no-glycine trial
1996). Respiration was measured at the end of the where low NHþ 4 concentrations existed (Rice and Tiedje
incubation by incubating 50 g dry weight equivalent soil 1989). The NO3 immobilization effect did not occur in the
in a sealed container with 20 ml 1 M NaOH traps for 3 days glycine trial because NHþ 4 limitations were drastically
(Zibilske 1994). reduced with glycine addition. In addition, higher rates of
Mixed bed ionic resin capsules (Unibest) were used in nitrification in the glycine trial likely occurred because this
experiments 2 and 3 to determine solution NHþ 4 ; NO3 , and
process was not limited by a lack of substrate availability
PO4 throughout the duration of the experiments. Capsules
(glycine additions resulted in high NHþ 4 concentrations).
were placed in the center of each pot, directly beneath each The higher rate of nitrification associated with charcoal
plant, and were removed and extracted in 10 ml of 2-M KCl in the glycine trial is consistent with the finding reported by
three consecutive times. We analyzed NHþ 4 ; NO3 , and
DeLuca et al. (2006), which suggests that charcoal may
PO4 from these extracts as described previously.
3
sorb compounds from litter extract and the soil solution that
Biol Fertil Soils (2007) 43:303–311 307
20 200
Amino N Amino N
a Amino N Charcoal *
b Charcoal ***
5 50
0 0
20 20
c Soluble Phenols
Soluble Phenols
d Soluble Phenols
KW test *
KW test **
Sorbed Phenols Sorbed Phenols Sorbed Phenols
Phenols (µg g-1)
15 15 Charcoal ***
Charcoal ***
Extract *** Extract **
Charcoal x Extract NS Charcoal x Extract NS
10 10
5 5
0 0
0.5 0.5
e f Respiration
Respiration (µg CO day )
Respiration
-1
Charcoal NS Charcoal NS
Extract * Extract NS
0.4 0.4
Charcoal x Extract NS Charcoal x Extract **
2
0.3 0.3
0.2 0.2
0.1 0.1
0.0 0.0
S S+E S+C S+C+E S S+E S+C S+C+E
are inhibitory to nitrifying bacteria, or sorb carbon-rich mechanisms for this pattern may differ between the two
molecules that would otherwise stimulate microbial immo- trials. In the no-glycine trial, the most likely explanation for
bilization of N. reduced NHþ 4 is that immobilization occurred as a function
A. uva-ursi extract had a strong positive effect on NHþ4 of N limitations in these soils. In the glycine trial, higher
in both no-glycine and glycine trials because it likely rates of nitrification associated with charcoal likely con-
contained some NHþ 4 and substrates that are rapidly tributed to lower NHþ 4 concentrations.
mineralized to NHþ 4 . Charcoal had a strong negative effect Both charcoal and extract significantly influenced con-
on NH4 in both no-glycine and glycine trials. The
þ
centrations of amino N that represent a highly labile
308 Biol Fertil Soils (2007) 43:303–311
Table 2 Plant mass and resin sorbed nutrients (mean±SE, n=20) from wood, such as lignin that are degraded during charcoal
a greenhouse experiment where soil was amended with 2% charcoal formation. It is unclear what effect these phenols have on
made from Douglas-fir (df) and ponderosa pine (pp) bark at 350°C
soil processes, but it is likely that they could be utilized as a
df pp no p food source by microbes, stimulating N immobilization.
Charcoal Charcoal Charcoal value Soil respiration showed little response to charcoal in
glycine or no-glycine trials. In the no-glycine trial, the extract
Total mass (g) a1.6 (0.2) a1.9 (0.1) b2.5 (1.0) <0.001
Root mass (g) a0.8 (0.1) a0.9 (0.1) b1.2 (0.1) <0.05
significantly increased soil respiration. Extract and charcoal
Aboveground a0.7 (0.1) b1.0 (0.1) c1.3 (0.1) <0.001 had no individual effect on soil respiration in the glycine trial;
mass (g) however, the interaction between charcoal and extract showed
Root to shoot a1.1 (0.1) b0.9 (0.1) b0.9 (0.1) <0.01 a significant effect. We speculate that this response may
ratio reflect that amines and degradable carbon substrates were
NHþ4 (μg resin a4.6 (0.9) b1.4 (0.6) b2.2 (0.8) <0.05 better utilized by microbes when phenolic molecules in the
capsule−1)
NO
3 (μg resin a1,770.8 b935.8 b581.5 <0.01 same extract were sorbed by charcoal.
capsule−1) (286.2) (241.9) (211.8) These data demonstrate that low-temperature charcoal
PO3
4 (μg resin a5.1 (1.4) a5.6 (0.9) b0.5 (1.2) <0.05 effectively sorbs soluble phenols from A. uva-ursi extracts,
capsule−1) which in turn stimulates nitrification, provided nitrification is
Letters in bold indicate differences using the Student–Newman–Keuls not substrate-limited. Our results are consistent with
post hoc procedure Berglund et al. 2004 and DeLuca et al. (2002), who showed
that the effect of charcoal on nitrification only occurred when
a labile N source was also present. These studies are also
consistent with the Terra Preta phenomenon reported in the
fraction of organic N that can be rapidly mineralized. Amazonian basin where charcoal and manure (high labile N
Glycine, which is a simple amino N molecule, stimulated concentration) were historically incorporated into the soil
rapid rates of N mineralization and resulted in increased (Glaser et al. 2001, 2002). Today, these soils maintain the
amino N concentrations, which suggests that the added highest fertility in the region, which may in part be a
glycine was not completely utilized and that substrate function of the interactive effect of charcoal and manure.
limitations were eliminated during this trial. In glycine and
no-glycine trials, the litter extract resulted in higher Experiment 2: effects of bark charcoal on plant growth
concentrations of amino N to soils. The effect of charcoal
on amino N, however, differed in glycine and no-glycine In this experiment, we unexpectedly found that charcoal
trials. In the no-glycine trial, charcoal significantly in- from both species diminished growth of K. macrantha
creased amino N concentrations. This response may have relative to the control with reduced mass in both above-
occurred because charcoal sorbed phenolic molecules that ground and belowground growth (Table 2). K. macrantha
otherwise would form insoluble complexes with amino N growing in pots with Douglas-fir charcoal had a signifi-
groups. In contrast, charcoal had a negative effect on amino cantly higher root to shoot ratio than the other treatments
N in the glycine trial, which is likely the result of charcoal that appeared to be primarily driven by low aboveground
enhancing microbial utilization of glycine. biomass. This data suggests that there is likely no difference
As expected, A. uva-ursi extract significantly increased in the effect of ponderosa pine and Douglas-fir charcoal on
phenols (soluble and sorbed) in both trials. The addition of plant species in this ecosystem.
charcoal to soil significantly diminished the soluble phenol We found that resin-sorbed NHþ 4 and NO3 were
concentration while increasing the pool of sorbed phenol. significantly higher in the Douglas-fir charcoal treatment
This result is consistent with several studies in the boreal relative to the ponderosa pine charcoal treatment and the
forest that have demonstrated a high capacity of charcoal to control. Resin-sorbed PO3 4 was significantly higher in both
adsorb phenolic compounds (Zackrisson et al. 1996; Wardle Douglas-fir and ponderosa pine charcoal treatments than
et al. 1998; DeLuca et al. 2002; Berglund et al. 2004). the control. These results may be interpreted in several
Solubility of these fractions likely influences the degree to ways. First, they may indicate higher mineralization and
which they are bioavailable and, therefore, their ability to nitrification rates in the presence of charcoal as suggested
interfere with N transformations (Harborne 1997). It is by experiment 1. If higher mineralization occurred in the
interesting to note that total phenols (sorbed and soluble) presence of charcoal, it is unclear why a corresponding
was higher in the charcoal-only treatment of both trials than increase in plant growth did not occur. It is possible that
the control, demonstrating that charcoal itself adds a some toxic substance was generated during charcoal
substantial amount of total phenol to the soil (Table 1). formation that inhibited root growth of K. macrantha,
These phenols are likely derived from the components of despite a positive effect on nutrient availability (Fritze et al.
Biol Fertil Soils (2007) 43:303–311 309
Table 3 Plant mass and resin sorbed nutrients (mean±SE, n=10) from a greenhouse experiment where soil was amended with 0, 0.5, 1, 2, 5, and
10% charcoal collected from a wildfire
Percent charcoal
0% 0.5% 1% 2% 5% 10% p
Total mass (g) a0.5 (0.2) ab1.0 (0.3) ab1.1 (0.2) ab1.1 (0.2) b1.3 (0.1) b1.4 (0.1) <0.05
Root mass (g) 0.3 (0.2) 0.6 (0.2) 0.7 (0.1) 0.7 (0.1) 0.8 (0.1) 0.8 (0.1) >0.05
Aboveground mass (g) a0.2 (0.1) ab0.4 (0.1) ab0.4 (0.1) ab0.4 (0.1) b0.5 (0.1) b0.6 (0.1) <0.01
Root to shoot ratio 1.5 (0.2) 1.5 (0.3) 1.8 (0.2) 1.7 (0.3) 1.6 (0.2) 1.3 (0.1) >0.05
−1
NHþ4 (μg resin capsule ) 55.6 (4.0) 49.8 (4.6) 36.9 (6.0) 42.7 (2.2) 43.0 (1.3) 44.4 (2.9) <0.05a
NO3 (μg resin capsule−1)
a1,539.8 b947.9 bc552.3 bc556.1 bc561.8 c248.6 <0.001
(463.4) (128.4) (116.3) (93.4) (278.7) (29.8)
−1
PO3
4 (μg resin capsule ) a10.1 (1.4) a8.8 (2.1) ab5.8 (1.2) ab6.5 (1.7) bc1.7 (1.0) c0.0 (1.2) <0.001
Letters in bold indicate differences using the Student–Newman–Keuls post hoc procedure
All p values are for one-way ANOVA, unless otherwise noted
a
Kruskal–Wallis test p value
1998; Villar et al. 1998). These toxic substances are likely may have offset this immobilization effect when wildfire
to be more abundant in low temperature charcoals, such as charcoal was used. Another potentially important difference
used in this experiment, and may be prone to volatilization is the different pH of laboratory charcoal and wildfire
at higher temperatures. An additional explanation is that charcoal (Table 1). The low pH associated with the lab
charcoal may have enhanced soil macroporosity, allowing charcoals may have indirectly diminished P availability
more soil solution to pass through capsules, resulting in in these treatments. Another difference between the
misleading resin-sorbed nutrient concentrations. charcoal used in experiments 2 and 3 was the range
of charcoal particle size used. Experiment 3 incorporated
Experiment 3: effect of wildfire charcoal on plant growth charcoal ranging from large (1–2 cm) to microscopic
fractions. We noted substantial root penetration into large
In support of our hypothesis, natural charcoal collected from a charcoal particles at the end of this greenhouse experiment,
wildfire showed a positive effect on growth of K. macrantha which suggests that some resource, such as water, is more
(Table 3). Both total and aboveground masses were signifi- available inside large charcoal particles. It is also possible
cantly higher in pots amended with 5 and 10% charcoal that grinding charcoal to a smaller size class, in some way,
addition than the control. Pots with lower charcoal content eliminates its beneficial effects on soil fertility. For
(0.5–2%) showed an intermediate growth response. No instance, grinding may enhance the availability of organic
significant shift in allocation to above- or belowground carbon because it is very immobile, whereas N ions are
structures was detected across the charcoal gradient. As in significantly more mobile; thus, nutrient immobilization
experiment 2, resin-sorbed NO 3 and PO4 decreased as plant
3
may be more substantial when charcoal is ground.
growth increased. These results suggest that these measure-
ments do not reflect any direct effect charcoal may have on
nutrient cycling, but are rather indicative of the solution nutrient Conclusion
concentration as influenced by plant uptake. No difference in
resin sorbed NHþ 4 occurred across the charcoal gradient. It is clear that charcoal has the potential to significantly alter
The different responses of K. macrantha to charcoal in soil solution chemistry and growth of K. macrantha. Charcoal
experiments 2 and 3 suggest that charcoal produced in a did not appear to stimulate N cycling in a low-nutrient
laboratory may be greatly different from charcoal generated setting, but when glycine was added to soil, charcoal greatly
during wildfire. Differences in charring conditions may enhanced N mineralization and nitrification. This result may
influence the chemical and structural nature of charcoal and indicate that low temperature charcoal contributes bioavail-
may therefore change its influence on soil solution able carbon that causes N immobilization under low nutrient
chemistry. One potentially important difference between conditions. As hypothesized, charcoal effectively sorbed
laboratory- and wildfire-collected charcoal was the ratio of soluble phenols from litter extracts. This sorption may
soluble phenols to NHþ 4 concentration extracted from the effectively reduce the inhibitory effect of litter extracts on
charcoals (Table 1). While all charcoal had relatively soil microorganisms, plants, and biogeochemical processes.
similar soluble phenol contents, which may stimulate Low-temperature, laboratory-generated charcoal had a nega-
microbial N immobilization, high NHþ 4 concentrations tive effect on growth of K. macrantha, possibly as a result of
310 Biol Fertil Soils (2007) 43:303–311
a toxicity effect caused by some compound formed during Glaser B, Lehmann J, Zech W (2002) Amerliorating physical and
low temperature charring or by N immobilization, as chemical properties of highly weathered soils in the tropics with
charcoal—a review. Biol Fertil Soils 35:219–230
suggested by the no-glycine soil incubation. In contrast, Gundale MJ, DeLuca TH, Fiedler CE, Ramsey PW, Harrington MG,
charcoal created during a wildfire had a positive effect on the Gannon JE (2005) Restoration management in a Montana
growth of K. macrantha, suggesting low-temperature, labo- ponderosa pine forest: effects on soil physical, chemical, and
ratory charcoal may not adequately represent field-collected biological properties. For Ecol Manag 213:25–38
Harborne JB (1997) Role of phenolic secondary metabolites in plants
charcoal. Field-collected charcoal may have been generated and their degradation in nature. In: Cadisch G, Giller KE (eds)
in a higher oxygen, higher temperature environment and may Driven by nature: plant litter quality and decomposition. CAB
have been exposed to leaching by rainwater and occlusion by International, Oxon, UK
soil organic compounds before collection. Further investiga- Hart SC, DeLuca TH, Newman GS, MacKenzie MD, Boyle SI (2005)
Post-fire vegetative dynamics as drivers of microbial community
tion is required to evaluate how charcoal formation conditions structure and function in forest soils. For Ecol Manag 220:166–184
alter its effect on soil processes and plant growth and how Kaye JP, Hart SC (1998) Ecological restoration alters nitrogen
these processes manifest themselves in natural ecosystems. transformations in a ponderosa pine-bunchgrass ecosystem. Ecol
Appl 8:1052–1060
Acknowledgements We thank V. Kurth, D. Mackenzie, and T. Kuo S (1996) Phosphorus. In: Sparks DL (ed) Methods of soil
Burgoyne for their assistance in the laboratory and greenhouse. We analysis. Part 3—chemical methods. SSSA Book Series 5. Soil
also acknowledge funding from the NSF (NSF-DEB-03171108) and Science Society of America, Madison, WI, pp 896–919
the USDA Joint Fire Sciences Program (FFS #107) for this research. Mann CC (2002) The real dirt on rainforest fertility. Science
297:920–923
Monleon VJ, Cromack K, Landsberg JD (1997) Short-and long-term
effects of prescribed underburning on nitrogen availability in
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DOI 10.1007/s11104-004-5485-5
Key words: adsorption, allelopathy, boreal forests, Empetrum hermaphroditum, germination, wood-
derived charcoal anatomy
Abstract
In Swedish boreal forests, areas dominated by the dwarf shrub Empetrum hermaphroditum Hagerup are
known for their poor regeneration of trees and one of the causes of this poor regeneration has been
attributed to allelopathy (i.e. chemical interferences) by E. hermaphroditum. Fire-produced charcoal is
suggested to play an important role in rejuvenating those ecosystems by adsorbing allelopathic com-
pounds, such as phenols, released by E. hermaphroditum. In this study, we firstly investigated whether
the adsorption capacity of charcoal of different plant species varies according to the wood anatomical
structures of these, and secondly we tried to relate the adsorption capacity to wood anatomical struc-
ture. Charcoal was produced from eight boreal and one temperate woody plant species and the adsorp-
tion capacity of charcoal was tested by bioassays technique. Seed germination was used as a
measurement of the ability of charcoal to adsorb allelochemicals. The charcoal porosity was estimated
and the pore size distribution was then calculated in order to relate the wood anatomical features to the
adsorption capacity. The results showed that the adsorption capacity of charcoal was significantly differ-
ent between plant species and that deciduous trees had a significantly higher adsorption capacity than
conifers and ericaceous species. The presence of macro-pores rather than a high porosity appears to be
the most important for the adsorption capacity. These results suggest that fire-produced charcoal has
different ability to adsorb phenols in boreal forest soil, and therefore may have differing effects on the
germination of seeds of establishing tree seedlings.
mechanical soil scarification on clear-cuts and nitrogen mineralization and stimulates soil micro-
has triggered the expansion and the dominance bial activity (Zackrisson et al., 1996). After a for-
of E. hermaphroditum (Zackrisson, 1977). E. her- est fire, up to 2000 kg ha)1 of wood charcoal is
maphroditum is today one of the most common produced (Zackrisson et al., 1996) and wood
species on northern inland clear-cuts (Data from charcoal produced by wild fire has similar prop-
the Swedish National Forest Survey) where it erties as commercially manufactured activated
through chemical interference causes tree regener- carbon (Bansal et al., 1988; Chereminisoff and
ation failures (Nilsson and Zackrisson, 1992). Ellerbusch, 1978). Fire-produced charcoal is thus
Allelopathy, which involves the release of sec- able to adsorb phenolic compounds released by
ondary plant metabolites, is a key process regu- ericoid plants (Zackrisson et al., 1996). However,
lating plant regeneration in many world the possible differential phenolic adsorption
ecosystems (e.g., Fisher, 1987; Keeley et al., capacities of charcoal produced by different
1985; Li and Romane, 1997; Pellissier, 1993; woody species have not been investigated before
Rice, 1979; Richardson and Williamson, 1988; whereas the wood anatomy varies between spe-
Waller, 1987; Wardle et al., 1998a). In the boreal cies (e.g., Hellberg and Carcaillet, 2003; Schwe-
forests of northern Sweden, E. hermaphroditum ingruber, 1990).
releases phenolic compounds, and in particularly The aim of the present study is (1) to deter-
the dihydrostilbene Batatasin-III, from green mine whether the charcoal from different plant
leaves and litter (Nilsson et al., 1998; Odén et al., species differs in its ability to adsorb allelopathic
1992; Wardle et al., 1998b; Zackrisson and Nils- compounds produced by E. hermaphroditum and
son, 1992) which inhibits seed germination and (2) to investigate whether this adsorption can be
seedling emergence, disturbs the plasmalemma related to the wood charcoal anatomy of individ-
integrity of target roots’ cells (Wallstedt et al., ual plant species. The ultimate aim of this study
2001) and negatively affects mycorrhizal symbio- is to contribute to a better understanding of the
sis of coniferous trees (Nilsson et al., 1993). Fur- functional role of fire-produced charcoal in the
ther, Batatasin-III impairs soil microbial activity boreal forest ecosystem.
and slows down decomposition which both con-
tribute to an increased accumulation of soil
organic material with time since last fire distur- Materials and methods
bance (DeLuca et al., 2002; Zackrisson et al.,
1996). Many phenolic compounds also form Plant species and production of charcoal
recalcitrant complexes with soil organic nitrogen
reducing the nitrogen accessibility to vascular Twigs of eight plant species abundant in the
plants (Bending and Read, 1996; Gallet and north European boreal forest were collected close
Lebreton, 1995; Wardle et al., 1998b). Therefore, to Umeå, northern Sweden (6349¢N; 2018¢E).
the phenol-regulated accumulation of humus and The species consisted of five angiosperms (Betula
the reduction of nitrogen available for plants pubescens Ehrh., Empetrum hermaphroditum Hag-
inhibit tree seedling establishment and growth of erup, Ledum palustre L., Populus tremula L. and
P. sylvestris (Nilsson and Zackrisson 1992; Zac- Vaccinium myrtillus L.) and three gymnosperms
krisson et al., 1996), one of the most commonly (Juniperus communis L., Picea abies (L.) H. Karst
occurring tree species in the European and the and Pinus sylvestris L.). In addition, twigs of
Asian boreal forests and one of the most impor- Ulmus minor Mill. were collected in southern
tant species for the forest industry. France (4226¢N; 310¢E). Ulmus minor has been
In field experiments, activated carbon has selected for its very large vessels (Jacquiot et al.,
been shown to adsorb phenols released by E. her- 1973) and therefore provides a better possibility
maphroditum vegetation and to eliminate the to test the effects of vessels size on the adsorption
inhibitory effects of E. hermaphroditum on tree capacity of charcoal.
seedlings establishment and growth (DeLuca Twigs of 3–4 mm in diameter from each spe-
et al., 2002; Nilsson, 1994; Thoss et al., 2004; cies were cut into segments of approximately
Zackrisson and Nilsson 1992). When added to 30 mm of length and were then left to dry at
field plots, activated carbon also increases humus room temperature for 1 month. Charcoal was
293
produced in a ‘‘muffle furnace’’ (Nabertherm, diameter). This latter procedure is reiterated for
L9/S27) according to the following protocol: the three replicates of burning. To each dish,
wood fragments of each species were put in an 25 P. tremula seeds (99.6% viability, stored
iron pan. Wood fragments from one species were at )18 C) are added on a Munktell No. 3 filter
separated from the others by vertically inserting paper. The inhibitory effect of the solution on
a glass slide into the pan. The position of wood P. tremula seeds was monitored and the number
samples was randomized in the pan and samples of germinated seeds was used as a measure of
were covered with sand to reduce the exposure to charcoal adsorption capacity (Zackrisson et al.,
oxygen during the burning process. This proce- 1996). To verify whether the charcoal itself might
dure facilitates production of charcoal and influence on P. tremula germination, five dishes
avoids total combustion of organic material and were set up with 2 mL of deionized water that
production of ashes. The pan was put in the muf- was soaked with 0.4 g of charcoal for 12 h; this
fle furnace for 35 min to reach 450 C and then experiment is performed for all species. The Petri
for an additional 15 min at 450 C after which dishes is placed in a climate chamber at 20 C
the charcoal samples were removed from the during 20 h per day of artificial illumination. The
muffle furnace. The selected temperature mimics total seed germination in each dish was recorded
the temperature at the ground surface during after 7 days.
wildfire (Chandler et al., 1983; Wiedemann et al.,
1988). Then, charcoal samples were sieved to Charcoal porosity: estimation and size of pores
retain material of 0.8–1.6 mm in size that corre-
sponds to the main size of soil charcoal (Carcail- In this study, pores were defined as all longitudi-
let and Talon, 2001). The burning procedure was nal cells that represent more than 95% of the
replicated three times for each species. total wood composition in the selected species,
i.e. the vessels, the fibres and the parenchyma in
Adsorption of allelopathic compounds angiosperms and most of the tracheids in gymno-
sperms (Figure 1). The porosity of charcoal is
The ability of charcoal to adsorb phenolic com- defined as a ratio between the total volume of all
pounds from an aqueous solution produced from pores and the total volume of wood. A transver-
green leaves of E. hermaphroditum was deter- sal section of each fragment of charcoal was used
mined by the use of a bioassay method following to estimate the charcoal porosity. The total area
Zackrisson and Nilsson (1992). In short, this covered by pores was measured within an obser-
method involved collecting green leaves of E. her- vation surface of 5250–5500 lm2. The ratio
maphroditum (At Rovågern, N. Sweden, 6350¢N; between the total area of all pores and the obser-
2015¢E), which were allowed to air-dry for 2 vation surface is performed for each species of
weeks. Deionized water was added to 50 g of dry charcoal to obtain a two-dimensional measure-
leaves per litre and the solution was agitated dur- ment of porosity called ‘transversal porosity’.
ing 48 h on a rotary shaker, and producing in This ratio serves to investigate whether the
this way a 5% weight/volume water extract. This adsorption capacity of charcoal is related to the
solution was then filtered through a Munktell porosity of charcoal. A high value of this ratio
No. 3 filter paper and diluted with deionized corresponds to a high charcoal porosity and con-
water to produce a 2% solution E. hermaphrodi- versely, a low value to a low charcoal porosity.
tum extract. This extract had a total inhibitory The charcoal porosity was measured on 10 trans-
effect on seed germination of Populus tremula versal sections for each species of charcoal.
seeds (see below). For each species of charcoal, The final ratio is thus based on the average of
0.4 g of charcoal fragments were added to 20 mL the 10 measurements by species of charcoal. All
of the 2% solution E. hermaphroditum and measurements were performed under an episcop-
placed on a rotary shaker for 12 h. Charcoal ic-analysing microscope (magnification: ·500).
fragments were then removed from the solution Values of surface were obtained with the image
by filtration through a filter paper (Munktell analysing software ‘OPTIMAS 5.2’. The pore
No. 3) and 2 mL of the remaining solution was area from each observation surface was used to
added to each of five Petri dishes (50 mm in test whether the pores size might be related to
294
Figure 1. Scanning electronic microscope (SEM) pictures of transversal sections of wood charcoal. All pictures are at the same
scale and magnification (·200). The top three pictures (ericoids) show small diameter vessels and fibres. Betula pubescens and Popu-
lus tremula have larger but less abundant vessels. Elm (Ulmus minor) has little but very large vessels. The porosity of the three gym-
nosperms (Juniperus communis, Picea abies and Pinus sylvestris) is mostly composed of tracheids with thin wall in the early wood
and thick wall in the late wood.
the adsorption capacity. The pores are classified ANOVA. Firstly, data relative to adsorption
according to the size of their area into micro- capacity of charcoal (Figure 3) was arsine square
pores (<50 lm2), meso-pores (from 50 to root transformed prior to analysis. ANOVA were
250 lm2) and macro-pores (>250 lm2). This performed to determine whether the adsorption
classification is based on the frequency of pores capacity of different species of charcoal was sig-
area per species (Figure 2). A ratio between nificantly different from each other. Significant
the total area occupied by each class of pores differences between species (P 0.05) were log10
and the transversal porosity was calculated. transformed and further analyzed by LSD test
The transversal porosity is thus defined as the (least significant difference). Secondly, ANOVA
sum of three areas i.e. micro-, meso- and macro- used to determine whether the transversal poros-
pores. Only charcoal produced from wood of ity of each species of charcoal was significantly
ericoı̈d plants (E. hermaphroditum, L. palustre different between species of charcoal (Figure 4).
and V. myrtillus) and broad-leaved deciduous Significant differences (P 0.05) between species
trees (B. pubescens, P. tremula and U. minor) are analyzed by Tukey test (honestly significant
were selected because conifers (gymnosperms) are difference). All statistics are computed with the
mostly composed of tracheids that do not show statistical package ‘SPSS 10.0’.
such a distinction between micro-, meso- and
macro-pores.
Results
Statistical analysis of data
The ability of charcoal to adsorb allelopathic com-
Homogeneity of variances (Levene test) of data pounds in E. hermaphroditum leaf water extract
was tested in accordance with the assumptions of differs significantly (ANOVA: F8.18 ¼ 9.633;
295
100
Populus
Betula
Ledum
Frequency of pores
80 Vaccinium
Empetrum
Ulmus
60
Meso-
pores Macro-
40 pores
20
Micro-
pores
0
0 50 100 150 200 250 300 350 400 500 1500 2500 3500
Figure 2. Frequency of pores per area of wood charcoal of different plant species.
100.0
A
Adsorption capacity of charcoal (%)
90.0
80.0
70.0
60.0
50.0
40.0 BC
B
30.0
BC
20.0
CD D CD
D
10.0 D
0.0
m
s
ris
is
s
re
or
s
a
en
itu
lu
un
ie
ul
st
st
in
til
c
ab
em
od
e
lu
m
es
.m
yr
lv
pa
m
hr
P.
ub
tr
sy
m
U
co
ap
P.
L.
.p
V.
P.
J.
rm
B
he
E.
Figure 3. Adsorption capacity of charcoal from different plant species measured as the mean (±SE) number of germinated Populus
tremula seeds. The shaded bars correspond to angiosperm and open bars to gymnosperms. Data are expressed as the percentage of
seeds germinated in deionised water (control). Bars topped with different letters are significantly different from each other at P 0.05
(LSD test following ANOVA).
P 0.001) between species (Figure 3). With the highest adsorbing capacity amongst the tested
exception of Juniperus communis, the adsorption plant species, i.e. about three times higher than
of allelopathic compounds by charcoal produced P. tremula and about 15 times higher than P. syl-
from broad-leaved deciduous trees (B. pubescens, vestris. Juniperus communis adsorbs allelopathic
P. tremula and U. minor) are higher than the compounds in the same range as B. pubescens and
adsorption by charcoal from ericoid species P. tremula. The overall lowest adsorption capaci-
(E. hermaphroditum, L. palustre and V. myrtillus) ties are found for charcoal produced from V. myrt-
and conifers (P. abies and P. sylvestris) (Figure 3). illus and P. sylvestris (<5% of germinated
Charcoal produced from U. minor wood shows the P. tremula seeds). Adsorption capacity of charcoal
296
80.0
B
70.0 BD
BCD BCD
40.0
30.0
20.0
10.0
0.0
m
ns
s
is
ris
e
a
r
es
o
lu
tr
ul
itu
un
in
ce
st
bi
s
til
m
lu
od
.m
m
ve
a
es
yr
re
pa
P.
hr
yl
m
ub
U
co
P.
s
ap
L.
V.
.p
P.
J.
m
B
er
h
E.
Figure 4. Mean (±SE) of transversal porosity of charcoal from different plant species expressed as percent of the relative total area
of pores in the wood. Shaded bars correspond to angiosperms and open bars to gymnosperms. Bars topped with different letters
are significantly different from each other at P 0.05 (Tukey’s HSD test following ANOVA).
produced from J. communis, B. pubescens, P. abies representing more than 75% of the transversal
and E. hermaphroditum are not significantly differ- porosity (Figure 6). For E. hermaphroditum and
ent from each other at P 0.05 (Figure 3). V. myrtillus, species with relatively low adsorp-
The overall transversal porosity varies tion capacity, the surface of the sum of
between 47 and 67% among the species (Fig- meso-pores ranges between 40 and 50% of the
ure 4). The highest transversal porosity is found transversal porosity. The percentage of micro-
for P. abies and the lowest for P. sylvestris. The pores does not differ between species and ranges
values are significantly different from each other between 20 and 40% (Figure 6). Examples of
at P 0.05 (ANOVA: F8.81 ¼ 7.986; P 0.001). transversal wood pattern of selected species are
The transversal porosity for P. sylvestris is signif- displayed in Figure 1.
icantly lower than the transversal porosity
(<55%) of the other species (Figure 4). The
transversal porosity of U. minor is also relatively Discussion
low, but is only significantly different from
V. myrtillus, E. hermaphroditum and P. sylvestris. The results of the present study show that char-
When transversal porosity is tested against the coal of different plant species has differing capac-
adsorption capacity of charcoal, no correlation ity to adsorb phenolic compounds released by
between the two is evidenced (Figure 5). E. hermaphroditum. The adsorption capacity of
The frequency of pores per transversal pore charcoal from U. minor, deliberately selected for
areas displays three classes of pores that differ its large pores (vessels), is about double than all
between species (Figure 2). For the broad-leaved other species (Figure 3). Amongst the angio-
deciduous trees, the surface corresponding to the sperms, the adsorption capacity is higher for
sum of macro-pores represents more than 50% charcoal produced from broad-leaved deciduous
of the transversal porosity (i.e. U. minor and trees than charcoal from ericoid species. Most
P. tremula) and almost 40% for B. pubescens Ericaceous species are characterized by small
(Figure 6). The species with the largest relative pores diameter, whereas broad-leaved trees have
amount of macro-pores are also the species with larger pores diameter (Figure 1). The adsorption
highest adsorption capacity (Figure 3). Macro- capacity of gymnosperm charcoal differs signifi-
pores are almost non-existent in L. palustre, cantly among the selected species. We expected,
which is mainly constituted of meso-pores however wrongly, the total surface of adsorption
297
90.0
80.0 U. m
Adsorption capacity of charcoal (%)
70.0
60.0
50.0
10.0 E. h P. a
L. p
P. s V .m
0.0
40 45 50 55 60 65 70
to be higher for those charcoal containing small macro-pores is generally higher for broad-leaved
diameter pores than those charcoal having large deciduous trees than for ericoid species where
diameter pores. This is because the relative macro-pores can be almost non-existent like in
porosity could have been lower when there was L. palustre (Figure 6). Charcoal species with a
a higher abundance of cell wall material. How- high density of macro-pores are also those with
ever, although different species differ in adsorp- the highest adsorption capacity, e.g., U. minor,
tion capacity (presumably due to wood anatom B. pub- escens and P. tremula (Figure 3 and 6).
ical differences), transversal porosity of the wood This observation suggests that a high adsorption
does not emerge as a driver of differences in capacity is linked with the total volume of macro-
adsorptive capacities among species because the pores. This result is strengthened by the observa-
process seems more complex and involves other tions of Chereminisoff and Ellerbusch (1978)
factors such as pore size distribution. If the total showing that adsorption capacities of charcoal
porosity was a significant factor explaining the were the results of both chemical and physical
adsorption, we should expect charcoal of P. properties. Macro-pores may have a lower surface
abies which had the largest transversal (Figure 4) tension than meso- and micro-pores, which should
to also have the largest adsorption capacity (Fig- in turn facilitate the penetration of water and dis-
ure 3), whereas this is not the case (Figure 5). solved compounds within charcoal.
Furthermore, the transversal porosity of P. abies Among the gymnosperms, J. communis and
and of P. tremula are not significantly different P. abies have a higher total porosity than P. syl-
from each other (Figure 4), while the adsorption vestris (Figure 4). SEM pictures (Figure 1) and
capacity is significantly different (Figure 3). literature on wood anatomy (Schweingruber,
The pore size distribution for each charcoal 1990) show that Pinus is generally characterized
species shows that the surface represented by by thick late wood relatively to the thickness of
298
100.0
90.0 Micro-pores
Meso-pores
Pore size distribution (%)
80.0
Macro-pores
70.0
60.0
50.0
40.0
30.0
20.0
10.0
0.0
m
ns
e
a
ro
lu
tr
ul
itu
in
ce
s
til
em
lu
.m
od
es
yr
pa
tr
hr
m
ub
U
P.
L.
ap
V.
.p
rm
B
he
E.
Figure 6. Pore size distribution in charcoal of six angiosperm species. Micro- ( lm2), meso- (50–250 lm2) and macro-porosity
(>250 lm2) are expressed as percentage of the total number of transversal pores of each species.
early wood, whereas Juniperus and Picea enced by other physical properties such as the
generally have a narrow late wood. Although the length of the pores (i.e. mostly length of vessels
diameter of conifer tracheids is relatively inde- for angiosperms and length of tracheids for gym-
pendent of the position within the tree ring, the nosperms), the density and the diameter of pit
wall thickness varies significantly which influ- orifices and the shape of the perforations that
ences the volume of the porosity. Our data indi- control the penetration of phenolic compounds
cate that species with a high proportion of late into charred cells.
wood material in their tree-rings appear to be To conclude, the present study supports previ-
linked to a lower adsorption capacity. ous work showing that fire-produced charcoal is
The differences in adsorption capacity able to regulate soil phenolic compounds released
between all species tested might also be influ- by E. hermaphroditum in the European boreal
enced by the presence of wood tar. Tar is forests (Pietikainen et al., 2000; Wardle et al.,
produced during the burning process and could 1998b; Zackrisson et al., 1996). Obviously, the
block the pores reducing the adsorption capac- simple volumetric process of adsorption occurs
ity of charcoal (www.fao.org/docrep/X5328f/ during the first days, but we stress the need to
x5328f00.htm#Contents) but also modify the understand the mechanism and kinetics of the
chemical properties of the charred surface. How- physico-chemical process of adsorption. The
ever, it is also likely that the different tree species identity of the plant producing the charcoal can
do not produce the same amount of tar during be important for determining the adsorption
the burning process, which also could explain capacity. Therefore, it is expected that variations
why the adsorption capacity is not linked to in seed germination and success of establishing
porosity. The presence of resins within conifers new trees seedlings are dependent on differences
trees might also influence the adsorption capacity in charcoal properties. It is likely that the regen-
of the charcoal produced, by modifying the inter- eration of trees is less important after a fire in
nal chemical structure of the pores. One of the areas dominated by ericoid species associated
limitations of the present study relates to the two with conifers than in areas dominated by broad-
dimensional estimation of the porosity that we leaved deciduous tree species notably those with
used. The adsorption by charcoal could be influ- large and abundant vessels, e.g., Ulmus, Quercus,
299
Fraxinus, Castanea in temperate forests and, Johnson E A 1992 Fire and vegetation dynamics: studies from
Salix, Populus, Betula and Sorbus in boreal the North American boreal forest. University Press, Cam-
bridge. 129 pp.
forests. The present study highlights the need for Keeley J E, Morton B A, Pedrosa A and Trotter P 1985 Role
conservation of broad-leaved deciduous trees in of allelopathy, heat and charred wood in the germination
boreal forests. of chapparal herbs and suffrutescents. J. Ecol. 73, 445–458.
Lehtonen H and Huttunen P 1997 History of forest fires in
eastern Finland from the fifteenth century AD – the possi-
ble effects of slash-and-burn cultivation. Holocene 7, 223–
Acknowledgements 228.
Li J and Romane F 1997 Effects of germination inhibition on
This research was funded through a European the dynamics of Quercus ilex stands. J. Veg. Sci. 8, 287–
294.
Union scholarship to Olivier Keech and the Niklasson M and Granström A 2000 Numbers and sizes of
French Centre National de la Recherche Scientif- fires: long-term spatially explicit fire history in a Swedish
ique (CNRS) to Christopher Carcaillet. boreal landscape. Ecology 81, 1484–1499.
Nilsson M C 1994 Separation of Allelopathy and Resource
Competition by the Boreal Dwarf Shrub Empetrum her-
maphroditum Hagerup. Oecologia 98, 1–7.
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BREVIA
Our results extend these findings by indicating
that charcoal can promote rapid loss of forest
humus and belowground C during the first dec-
Fire-Derived Charcoal Causes Loss of ade after its formation. Fire often causes sub-
stantial losses of ecosystem C, and our results
Forest Humus provide evidence for a previously unreported mech-
anism that could contribute to these losses. Our
results are specific to boreal forests and to the type
David A. Wardle,* Marie-Charlotte Nilsson, Olle Zackrisson of charcoal that we used, and further work is
needed to determine the importance of this mech-
oreal forests serve as important global versus Mix (exp)]. Further, nitrogen immobi-
B
anism in other biomes and for other types of
sources or sinks of carbon (C), and wild- lization was less than expected in the mixture charcoal (11). Although several studies have
fire is a major driver of C storage in these bags (Fig. 1). For these measurements, substrate recognized the potential of black C for enhancing
forests. Although fire releases CO2 to the atmo- mixing effects [i.e., values for (observed – expected)/ ecosystem C sequestration (2, 3), our results
sphere, it also converts plant biomass into forms expected] never differed significantly across the show that these effects can be partially offset by
of black carbon, such as charcoal, that are resist- three sites [P value always greater than 0.20 its capacity to stimulate loss of native soil C, at
ant to microbial attack and persist in the soil for according to analysis of variance (ANOVA)]. This least for boreal forests. The effect of charcoal on
thousands of years (1). It has frequently been result is despite the sites differing in both stand native soil C needs to be explicitly considered to
Fig. 1. Changes in litterbag properties over a 10-year period. Humus, Charcoal, average of all three sites with 11 replicates per site, and vertical bars are mean
and Mix (obs) correspond to litterbags containing pure humus, pure charcoal, and within-site standard error. For all measurements at all dates and sites, values for
a 50:50 mixture of charcoal and humus, respectively. Mix (exp) corresponds to Mix (exp) and Mix (obs) differ significantly at P = 0.01 (paired t tests). (A) Total
expected values for litterbags containing 50:50 mixtures of charcoal and humus if mass loss. (B) SIR. (C and D) Loss of C and N from litter bags (per unit initial mass)
no interactive effects between the components occur (6). Each data point is the over 10 years; negative values in (D) reflect net N gain through immobilization.