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Chemosphere 78 (2010) 1167–1171

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Chemosphere
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Technical Note

Agronomic properties of wastewater sludge biochar and bioavailability of metals


in production of cherry tomato (Lycopersicon esculentum)
Mustafa K. Hossain a, Vladimir Strezov a,*, K. Yin Chan b, Peter F. Nelson a
a
Graduate School of the Environment, Faculty of Science, Macquarie University, NSW 2109, Australia
b
NSW Department of Primary Industries, Locked Bag 4, Richmond, NSW 2753, Australia

a r t i c l e i n f o a b s t r a c t

Article history: This work presents agronomic values of a biochar produced from wastewater sludge through pyrolysis at
Received 31 October 2009 a temperature of 550 °C. In order to investigate and quantify effects of wastewater sludge biochar on soil
Received in revised form 7 January 2010 quality, growth, yield and bioavailability of metals in cherry tomatoes, pot experiments were carried out
Accepted 8 January 2010
in a temperature controlled environment and under four different treatments consisting of control soil,
soil with biochar; soil with biochar and fertiliser, and soil with fertiliser only. The soil used was chromo-
sol and the applied wastewater sludge biochar was 10 t ha 1. The results showed that the application of
Keywords:
biochar improves the production of cherry tomatoes by 64% above the control soil conditions. The ability
Biochar
Chromosol soil
of biochar to increase the yield was attributed to the combined effect of increased nutrient availability (P
Pyrolysis and N) and improved soil chemical conditions upon amendment. The yield of cherry tomato production
Wastewater sludge was found to be at its maximum when biochar was applied in combination with the fertiliser. Application
of biochar was also found to significantly increase the soil electrical conductivity as well as phosphorus
and nitrogen contents. Bioavailability of metals present in the biochar was found to be below the Austra-
lian maximum permitted concentrations for food.
Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction potential to increase conventional agricultural productivity


(McHenry, 2009). Understanding of agricultural effects of biochar
Sludge wastes produced during wastewater treatment are some is very limited and based on few biomass feedstock materials.
of the most difficult waste materials to manage due to the increas- Previous work investigated the beneficial effects of biochar pro-
ing quantities produced and the pathogenic organisms and metal duced from green-waste and poultry litter on the yield of agricul-
contents present in the sludge. Approximately 190 000 t of bioso- tural crop and properties of soil (Glaser et al., 2002b; Chan et al.,
lids are produced each year at wastewater treatment plants in 2007, 2008). It was found that biochar from poultry litter signifi-
the Sydney basin alone (Bamforth et al., 2004). The safe and bene- cantly improves the yield of radish crops (Chan et al., 2008) but
ficial use of wastewater sludge is a subject of considerable interest the risk of using poultry as a soil amendment is still unknown. Bio-
for the society. Application of unprocessed wastewater sludge and char addition to soils also improved nitrogen fertiliser use effi-
wastewater sludge compost have been previously trialled as ciency through improvement of the chemical properties of
organic fertilisers with some success (Singh and Agrawal, 2007; chromosol soil. Application of biochar to the soil was found to in-
Roca-Perez et al., 2009). Thermal processing of wastewater sludge crease soil cation exchange capacity (CEC) by up to 40% and soil pH
provides an additional option to manage this waste and for its by up to one pH unit (Mikan and Abrams, 1995). The application of
upgrading to bio-gas, bio-oil and biochar (Werther and Ogada, wastewater sludge biochar as a soil amendment has a potential to
1999; Inguanzo et al., 2002; Hossain et al., 2009). The biochar is provide a viable option for nutrient recovery when applied to soils,
particularly attracting international attention for the following improve the wastewater sludge management practice and seques-
two reasons. Firstly, biochars can be used as soil amendments for ter carbon in the soils.
improving soil properties and crop yield and secondly, storing However, there is currently no published data available on
biochars in soils is regarded as means for permanently sequester- quantification of the effect of wastewater sludge biochar to the soil,
ing carbon (Glaser et al., 2002a,b; Lehmann et al., 2003, 2006). plant nutrients and the bioavailability of metals in plant. This study
The conversion of wastes by pyrolysis to produce biochar has is focused on the agronomic potential of wastewater sludge bio-
char and its impact on soil quality, plant growth, yield and bio-
* Corresponding author. Tel.: +61 2 9850 6959; fax: +61 2 9850 7972. availability of metals in fruit using cherry tomato (Lycopersicon
E-mail address: vstrezov@gse.mq.edu.au (V. Strezov). esculentum) as an agricultural crop in a glasshouse pot experiment.

0045-6535/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.chemosphere.2010.01.009
1168 M.K. Hossain et al. / Chemosphere 78 (2010) 1167–1171

2. Materials and methods In each pot 6 kg of air-dried soil was packed and the applied
biochar was 10 t ha 1. In absence of standards or recommended
2.1. Soils application dose of biochars to soils, the amount of biochar applied
in this research is based on previous investigations conducted by
The soil used for this study was collected from the flat paddock Chan et al. (2008) and Van Zwieten et al. (2009) who demonstrated
at the Centre for Recycled Organic Agriculture site Menangle near benefits to soil and plants by application of 10 t ha 1 of biochar
Camden, south-western region of Sydney, Australia. The soil se- produced from papermill sludge and poultry litter, respectively.
lected was with fair agricultural properties in order to better deter- The fertiliser application used in the current experiment was
mine the effect of treatment conditions using biochar on plant equivalent to 120 kg of nitrogen; 70 kg of phosphorus and 80 kg
growth and production. According to the Australian Soil Classifica- of potassium ha 1 (Murrison and Huett, 1987).
tion, the soil collected for this research is classified as chromosol The pots were wetted up to the field capacity using de-ionised
(Isbell, 1996). A composite sample was collected down to 0.1 m water. Five seeds of tomato were sown in each pot and germinated
of the top soil layer, followed by sieving through a 6 mm sieve. for 5–6 d. After 15 d the germinated seedlings were thinned and
The chemical properties of the collected surface soil are shown in the healthiest plant from each pot was retained. A shallow tray
Table 1. The soil was found to be low in total nitrogen (0.13%), was placed under each pot and the plants were watered approxi-
ammonium nitrogen (3.6 mg kg 1), phosphorus (15 mg kg 1) and mately up to the field capacity throughout the duration of the trial.
was found to be acidic in nature. The pot trials were carried out for a total of 16 wk.

2.2. Biochar preparation 2.4. Soil and fruit analysis

The feedstock used for biochar production for this study was The soil from each pot was collected and air-dried at a temper-
wastewater sludge collected from a wastewater treatment plant ature of 36 °C until constant weight. The soils from each pot were
in Sydney region, Australia. The wastewater sludge was first air- mixed and passed through a 4 mm sieve to separate the plant deb-
dried and then pyrolysed under controlled conditions to ensure ris. Sub-samples were further ground to pass through a 2 mm sieve
uniform heating and treatment conditions. Biochar production and analysed for electrical conductivity (EC), pH, total nitrogen,
was carried out using a fixed bed reactor set at a heating rate of extractable phosphorus (Colwell), exchangeable cations and CEC.
10 °C min 1 up to 550 °C. Nitrogen gas was flown through the sam- Total N were measured by Dumas combustion method using an
ple at a rate of 100 mL min 1 to ensure inert heating conditions. Elementar vario MAX CN analyser with combustion chamber set
Approximately 300 g of wastewater sludge biochar were pyrolysed at 900 °C and oxygen flow rate of 125 mL min 1. The pH was mea-
with each experiment. The pyrolysis trials were repeated to sured in 0.01 M CaCl2 (1:5) according to method 4B2 of Rayment
achieve a total of 1 kg of biochar which was then used for chemical and Higginson (1992). Available phosphorus (Colwell), mineral
analysis and pot experiments. The chemical properties of the nitrogen (KCl extraction and extractable) and micronutrients were
wastewater sludge biochar used in this experiment are shown in measured according to methods 9B1, 7C2 and 12A1 of Rayment
Table 1. The biochar was found to be alkaline in nature (pH 8.2) and Higginson (1992), respectively. Exchangeable cations were
and low in total nitrogen (2.3%). determined using the Gillman and Sumpter (1986) method. At
the end of the pot experiment the fruits and plants were harvested
2.3. Pot trial from each pot and oven dried at 70 °C to constant weight before
weighing to determine the dry matter.
Glasshouse pot trial using L. esculentum as a crop species were Accumulation of metals and trace elements in fruits were ana-
carried out to determine the agronomic properties and the effect lysed by ICP according to the US EPA method 6010. The samples
of the wastewater sludge biochar on growth, yield and risk of met- were homogenised and a sub-sample (0.2–0.5 g) was digested with
als. The pot trials were carried out in a temperature controlled (20– re-distilled nitric acid on a DigiPrep block for 1 h until vigorous
26 °C) glasshouse environment. Cylindrical plastic pots 19 cm in reaction was complete. Samples were then transferred to a Mile-
height, 15 cm in diameter at the bottom and 20 cm in diameter stone microwave for further digestion. The digested sample was
at the top were used for the pot trials. The experimental design analysed for metals and trace elements using ICP-AES.
was factorial randomised block design with four treatments and
six replications. The four treatments were: (i) control soil (CP); 2.5. Statistical analysis
(ii) soil with biochar (SB); (iii) soil with biochar and fertiliser
(SBF) and (iv) soil with fertiliser (SF). All data were statistically studied by analysis of variance using
GENSTAT 9.1 software (Lawes Agricultural Trust, 2006). The treat-
Table 1 ment means were compared using least significant differences for
Chemical properties of soil and biochar used in pot experiment. the main effect of biochar on plant growth properties. Unless
otherwise stated, the differences were significant at p 6 0.05 level.
Properties Unit Soil Biochar
EC dS m 1 0.09 1.9
pH (CaCl2) pH unit 4.6 8.2 3. Results
Total N % 0.13 2.3
P (Colwell) mg kg 1 15 1100 3.1. Effect of biochar application on soil parameters
Ammonium N (KCl extract) mg kg 1 3.6 11
Nitrate N (KCl extract) mg kg 1 4.9 0.49
Table 2 shows the changes of chemical properties of the soils of
Exchangeable cations
Al cmol kg 1
0.37 <0.03
different treatments due to application of biochar. Application of
Ca cmol kg 1
5 33 wastewater sludge biochar was found to significantly change most
1
Mg cmol kg 1.5 1.8 of the chemical properties of the soil. The biochar increased EC, pH,
1
K cmol kg 0.17 0.24 total nitrogen, extractable phosphorus and CEC of the soil. EC was
1
Na cmol kg 0.2 0.5
1 found to have the highest value (0.53 dS m 1) in SBF treatment
CEC cmol kg 7.2 35
while pH was the highest (pH 4.7) in the SF treatment. SBF treat-
M.K. Hossain et al. / Chemosphere 78 (2010) 1167–1171 1169

Table 2
Changes in soil chemical properties and standard deviation by biochar application.

Properties Unit CP SB SBF SF LSD


1
EC dS m 0.05 (±0.00) 0.29 (±0.03) 0.53 (±0.04) 0.33 (±0.04) 0.14
pH pH unit 4.3 (±0.01) 4.5 (±0.03) 4.7 (±0.06) 4.7 (±0.06) 0.13
Total N % 0.14 (±0.01) 0.18 (±0.01) 0.22 (±0.01) 0.19 (±0.01) 0.02
P (Cowell) mg kg 1 26 (±0.87) 56 (±2.4) 290 (±24.2) 303 (±16.0) 36
Ammonium N (KCl extract) mg kg 1 3.6 (±0.27) 5.1 (±0.57) 102 (±20.1) 88 (±19) 41
Nitrate N (KCl extract) mg kg 1 9.3 (±1.26) 54 (±21.6) 193 (±19.6) 125 (±23.7) 64
Exchangeable cations
1
Al cmol kg 0.38 (±0.01) 0.23 (±0.01) 0.08 (±0.01) 0.09 (±0.01) 0.04
1
Ca cmol kg 4.7 (±0.07) 5.9 (±0.1) 6.5 (±0.11) 6.0 (±0.1) 0.3
1
Mg cmol kg 1.6 (±0.03) 1.6 (±0.02) 1.4 (±0.04) 1.6 (±0.02) 0.1
1
K cmol kg 0.28 (±0.02) 0.25 (±0.09) 1.3 (±0.16) 1.3 (±0.09) 0.35
1
Na cmol kg 0.39 (±0.01) 0.39 (±0.03) 0.29 (±0.03) 0.38 (±0.01) 0.07
1
CEC cmol kg 7.3 (±0.09) 8.5 (±0.14) 9.5 (±0.18) 9.4 (±0.17) 0.45

LSD = least significant difference.

ment contained the highest concentration of total nitrogen (0.22%). 120

Dry matter (gm/plant)


The available phosphorus (Cowell) exhibited the highest value a
100
(303 mg kg 1) in case of the SF treatment but it was not signifi-
cantly different to the SBF treatment at 290 mg kg 1. A significant 80
increase of mineral nitrogen was detected in the SBF treatment 60
(Table 2). For the exchangeable cations, the biochar application in- 40
creased only the calcium concentration, while the aluminium de-
creased in all treatments. 20
0
3.2. Effect of biochar on plant height
250
Fruits number/plant

b
The height of each plant in all treatments was measured start- 200
ing from wk 5 to 15. The results, as shown in Fig. 1, revealed signif-
icant effect of biochar on the height of the plant. However, SBF 150
treatment conditions showed the highest average performance 100
(69.3 cm), followed by SF (64.0 cm), SB (57.7 cm) and CP
(44.5 cm). The maximum plant height at the end of 15 wk trial 50
was estimated at 96.8 cm for CP, 107.5 cm for SB, 113.5 cm for 0
SBF and 109 cm for SF conditions. The maximum plant growth rate
was observed during the 8th wk for SBF (13.0 cm), the 9th wk for 3000
SF (13.5 cm), and 12th wk for SB (15.8 cm). c
Yield (gm/plant)

2500
2000
3.3. Effect of biochar on plant dry matter weight
1500
The dry matter weight of cherry tomato plant shoot varied sig- 1000
nificantly among the different treatments, as shown in Fig. 2a. The 500
average dry weight of shoot production ranged from 61.9 g plant 1 0
for CP to 92 g plant 1 recorded for SBF treatment. There was no CP SB SBF SF
significant difference between the SB (73.8 g plant 1) and SF Treatments
(79.7 g plant 1) treatments. The SBF treatment showed the highest
performance due to the addition of fertiliser in combination with Fig. 2. Cherry tomato production using different soil treatments: (a) dry matter
biochar, which improved the growth of the cherry tomato plant. production of cherry tomato per plant; (b) cherry tomato fruit number; (c) cherry
tomato yield.

CP 3.4. Effect of biochar on the number of produced fruits


120
100 SB The cherry tomato fruits produced from the plants for all of the
SBF
height (cm)

considered treatments were harvested during a period of 12–


80
SF 16 wk. All plant treatments using biochar, fertiliser or combination
60 of both, exhibited larger number of fruits per plant, comparing to
CP condition (Fig. 2b). Plants grown with SBF had the maximum
40
average fruit number which was 167% above the CP condition,
20 63% above SB and 122% above SF treatments.
0
5 6 7 8 9 10 11 12 13 14 15 3.5. Effect of biochar on crop yield
weeks
Biochar in combination with fertiliser also showed the most sig-
Fig. 1. Weekly plant height of cherry tomato. nificant effect on the yield of cherry tomato production followed by
1170 M.K. Hossain et al. / Chemosphere 78 (2010) 1167–1171

SF and SB treatments, as shown in Fig. 2c. The maximum average chromosol soil for improvement of the yield of cherry tomato pro-
yield per plant was harvested from SBF conditions, (2514 g) which duction by 64%. This value is of a similar magnitude to the yield ob-
was 20% greater than the case of SF conditions and 97% above the served for radish using poultry litter biochar when applied at the
yield produced in SB conditions. CP produced the lowest (776 g) same dose on a similar soil (Chan et al., 2008). The lower agricul-
yields of cherry tomatoes. The difference in crop yield between tural properties of the soil used in the pot experiment was due
CP and SB conditions was also significant (Fig. 2c). SB treatment to the low nutrient availability of the chromosol soil selected for
produced 64% greater yield compared to control treatment. the study (Table 1). It was observed that the average fruit yield
produced under the control treatment conditions was lower and
plants were thinner than the fruits and plants from the other treat-
3.6. Heavy metal concentrations in fruits
ments. The weight of the dry shoot (Fig. 2a) and the number of
fruits (Fig. 2b) produced from CP treatment were also lower than
The accumulation of heavy metals, especially arsenic, cadmium,
under the remaining treatment conditions.
chromium, copper, lead, nickel, selenium and zinc, are of great con-
It has been already identified that biochar applied to soils im-
cern in agricultural product due to potential threat for human and
proves the availability of phosphorus, total nitrogen and major cat-
animal health. The amount of heavy metals present in the applied
ions (Glaser et al., 2002b; Lehmann et al., 2003). Additionally,
biochar and their bioavailability in fruits are shown in Table 3.
biochar has positive liming effect when applied to low pH soils
There were 16 metals and trace elements measured in the waste-
(Van Zwieten et al., 2007), thereby the application of biochar to
water sludge biochar. The results of fruit analysis show that all ele-
acidic soils increases the soil pH and thereof improves nutrient
ments are uptaken by the fruits but their amounts are not
use efficiency. Our study shows significant improvement in the
significant. The presence of selenium (<0.05), lead (<0.01) and tin
number of fruits per plant when biochar was applied at 10 t ha 1
(<0.05 mg kg 1) are below the detection limit in all treatments.
to the chromosol with low pH soil (Fig. 2b), suggesting release of
In the SBF treatment the presence of arsenic (<0.01) and chromium
additional nutrients from the biochar. The wastewater sludge bio-
(<0.05 mg kg 1) in the fruit are also below the detection limit. The
char used in the current work was high in extractable phosphorus
accumulation of cadmium in fruit was estimated at 0.85% for both
(1100 mg kg 1). Presence of phosphorus in soils is particularly fa-
SB and SBF treatments, and 1% in case of the SF treatment. Silver
voured for growth of a tomato root system increasing fruit produc-
(<0.01 mg kg 1) is less than detection limit in SB and CP treat-
tivity (Filgueira, 2000). According to Poulton et al. (2002) soil with
ments. Copper and zinc show the lowest bioavailability in the
high phosphorus content improves vegetative and reproductive
SBF treatment followed by SB and SF treatments. Availability of
traits of tomato plants, therefore additional phosphorus has an
the other trace elements in the fruit was estimated as very low (Ta-
important role in incremental fruit formation when biochar is
ble 3). Only the concentration of cadmium present in the fruit for
added to the soil. The wastewater sludge biochar produced for this
SF treatment conditions was found to be equivalent to the Austra-
work had a higher level of total nitrogen (2.3%) while the mineral
lian maximum permitted concentration of cadmium in food. How-
nitrogen was low at 0.49%. This suggests that the wastewater
ever, the remaining metals, including antimony, arsenic, cadmium,
sludge biochar might have the ability to increase mineralisation
copper, lead, mercury, selenium, tin and zinc, were measured be-
of soil organic nitrogen upon its incorporation into soil as a result
low the Australian maximum permitted concentrations for food
of priming effect (Hamer et al., 2004). Another possibility for
products (Table 3).
improvement of the nitrogen release is through the mineralisation
of wastewater sludge biochar and therefore release of the available
4. Discussion nitrogen after addition to soil during the pot experiments. The car-
bon and nitrogen ratio of the biochar used in the pot trials was only
Results obtained from the pot experiments in this work indicate 8.7 (Table 1), therefore mineralisation is expected upon its applica-
the potential of the application of wastewater sludge biochar to a tion to soil (Sullivan and Miller, 2001). According to Hamer et al.
(2004), biochars from maize and rye residues in soils can promote
mineralisation of carbon compounds as well as biochar by enhanc-
Table 3
ing the growth of micro-organisms.
Concentration (mg kg 1) of heavy metals and trace elements in wastewater sludge
biochar and their accumulation in fruits of four different treatments comparing to The highest yield of cherry tomato in the current work was har-
Australian food standard limitations for heavy metals in food (mg kg 1). vested from the combined biochar with fertiliser treatment
(2514 g plant 1) which was 20% above the yield produced under
Elements Biochar Treatments Present Australian MPCa
the SF treatment. Since the nutrient addition through a fertiliser
CP SB SBF SF
was optimal for cherry tomato growth and production, the im-
Arsenic 8.8 0.02 0.02 BDL 0.01 1.0 proved yield observed in the combined biochar and fertiliser treat-
Cadmium 4.7 0.03 0.04 0.04 0.05 0.05–2.0
ment, when compared to fertiliser only, suggests additional
Chromium 230 BDL BDL BDL 0.06 –
Copper 2100 5.9 6.2 4.6 6.2 10–70 beneficial effects of biochar inclusion, which are beyond the sole
Lead 160 BDL BDL BDL BDL 1.5–2.5 nutrient effect. These additional benefits include improved soil
Nickel 740 8.2 1.2 0.61 0.55 – properties as well as the liming effects. The fertiliser effect of bio-
Selenium 7 BDL BDL BDL BDL 1.0 char is additionally supported by increased water retention and
Zinc 3300 18 22 18 22 150
Antimony 8 BDL 0.01 BDL BDL 1.5
CEC of the soil by the large surface area of the biochar (Steinbeiss
Boron 20 15 15 9.6 15 – et al., 2009).
Silver 29 BDL BDL 0.01 0.01 – Biochar produced from wastewater sludge pyrolysis has poten-
Barium 750 3.6 0.91 0.35 2.9 – tial to reduce the quantity of fertiliser requirement for cultivation
Beryllium 1 BDL BDL BDL BDL –
of agricultural crops, however application of wastewater biochar at
Cobalt 21 0.06 0.03 0.3 0.27 –
Tin 310 BDL BDL BDL BDL 50 10 t ha 1 can not fully substitute for the requirement of fertilisers.
Strontium 390 5 3.1 2.6 4.6 – The composition of sewage sludge is variable and contains toxic
metals (Smith, 1992) which limit the land application due to food
MPC = maximum permitted concentration.
BDL below detection limit of <0.05 mg kg 1 for As, Cr, Se and Sb, and <0.01 mg kg 1 chain contamination (Chaney, 1990). Singh and Agrawal (2007)
for Pb, Sb and Be. found increased concentrations of Pb, Cr, Cd, Cu, Zn and Ni in Beta
a
Source: Anon (1987). vulgaris (leafy vegetables) when grown in a greenhouse environ-
M.K. Hossain et al. / Chemosphere 78 (2010) 1167–1171 1171

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black carbon and glucose mineralization. Org. Geochem. 35, 823–830.
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2009). Metal behaviour in soils and plant uptake are dependent pyrolysis of sewage sludge: the influence of pyrolysis conditions on solid, liquid
and gas fractions. J. Anal. Appl. Pyrol. 63, 209–222.
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