Article

pubs.acs.org/est

Transformation, Morphology, and Dissolution of Silicon and Carbon

in Rice Straw-Derived Biochars under Dierent Pyrolytic
Temperatures
Xin Xiao,, Baoliang Chen,*,, and Lizhong Zhu,

Department of Environmental Science, Zhejiang University, Hangzhou, Zhejiang 310058, China

Zhejiang Provincial Key Laboratory of Organic Pollution Process and Control, Hangzhou, Zhejiang 310058, China
*
S Supporting Information

ABSTRACT: Biochars are increasingly recognized as environ-

mentally friendly and cheap remediation agents for soil pollution.
The roles of silicon in biochars and interactions between silicon and
carbon have been neglected in the literature to date, while the
transformation, morphology, and dissolution of silicon in Si-rich
biochars remain largely unaddressed. In this study, Si-rich biochars
derived from rice straw were prepared under 150700 C (named
RS150-RS700). The transformation and morphology of carbon and
silicon in biochar particles were monitored by FTIR, XRD, and SEM-
EDX. With increasing pyrolytic temperature, silicon accumulated, and
its speciation changed from amorphous to crystalline matter, while the
organic matter evolved from aliphatic to aromatic. For rice straw
biomass containing amorphous carbon and amorphous silicon,
dehydration (<250 C) made silicic acid polymerize, resulting in a closer integration of carbon and silicon. At medium
pyrolysis temperatures (250350 C), an intense cracking of carbon components occurred, and, thus, the silicon located in the
inside tissue was exposed. At high pyrolysis temperatures (500700 C), the biochar became condensed due to the
aromatization of carbon and crystallization of silicon. Correspondingly, the carbon release in water signicantly decreased, while
the silicon release somewhat decreased and then sharply increased with pyrolytic temperature. Along with SEM-EDX images of
biochars before and after water washing, we proposed a structural relationship between carbon and silicon in biochars to explain
the mutual protection between carbon and silicon under dierent pyrolysis temperatures, which contribute to the broader
understanding of biochar chemistry and structure. The silicon dissolution kinetics suggests that high Si biochars could serve as a
novel slow release source of biologically available Si in low Si agricultural soils.

INTRODUCTION
Biochar is a carbon-rich material that is produced during the
pyrolysis of biomass in the presence of little or no oxygen.14
Recently, biochars have received much attention as carbon-
negative products1 and eective adsorbents.5 Biochar amend-
ment of soil is viewed as a new opportunity for mitigating
global warming and as a strategy to improve soil health and
productivity.1,6,7 Biochars have several unique properties, which
allow them to improve the soil cation exchange capacity
(CEC), adjust pH, retain water and fertilizer,8 reduce
greenhouse gas emissions,9,10 increase carbon stability in
soil,11,12 and enhance the sorption capacity for organic
pollutants3,1315 and heavy metals.1618 Therefore, biochar is
thought to be an environmentally friendly and cheap
remediation agent for soil pollution and soil carbon
sequestration.
As a heterogeneous structural material, biochar contains
carbon components and ash fractions; however, the structure of
its carbon components has been the area of focus in research.
Generally, carbon components in biochars contain water-
soluble organics, high-molecular-weight aliphatic compounds,
and a relatively high proportion of insoluble aromatic
structures.19,20 The soluble and low-molecular-weight organic
compounds mineralize faster than aliphatic and condensed
aromatic structures.21 Actually, aliphatic carbons such as
carbohydrates and alkyls can derive to aromatic systems
through reactions of condensation when they are subjected to
pyrolytic conditions. As a result, aromatic carbon was more
recalcitrant than aliphatic carbon.22,23 Furthermore, the
characteristics of biochars heavily depend on the pyrolysis
temperature and various precursor feedstocks.19,2426 High-
temperature biochars contain more aromatic carbon than low-
temperature biochars, which makes the former more inert.22,23
The structure of carbon components usually determines the
stability of biochars and their adsorptive properties. Chen et al.3
Received: December 20, 2013
Revised: February 12, 2014
Accepted: February 24, 2014
Published: February 24, 2014

2014 American Chemical Society 3411 dx.doi.org/10.1021/es405676h | Environ. Sci. Technol. 2014, 48, 34113419
Environmental Science & Technology
found that the sorption mechanisms of organic pollutants to
biochars varied from partitioning-dominant at low carbon-
ization temperature to adsorption-dominant at high carbon-
ization temperature. For middle pyrolytic temperature biochars,
the uncarbonized organic matter was colocalized with the
carbonized matter;14 thus, the biochar displayed a slow sorption
rate for organic pollutants,26 and sorption was promoted by use
of a cosolute and elevated solution temperature.14
To date, the transformation, morphology, and dissolution of
silicon in Si-rich biochars have been largely unaddressed. For
example, rice straw contains 13.87% ash content, of which SiO2
accounts for approximately 56.23% by weight.27 In fact, silicon
is not only a metal coprecipitator28,29 but also an important
substance in the formation of inorganic crystals within biochars.
Recently, Qian and Chen found that the eective alleviation of
aluminum phytotoxicity to wheat by manure-derived biochar
was due to the coprecipitation of Al with silicate particles.28,29
Available silicon content in soil, which is released from the
dissolution of silicate minerals in the form of silicic acid,30,31 is
an important nutrient for the growth of silicophilic plants (such
as rice, maize, wheat, and barley).30 Many arable lands in the
world, including those in China, suer from silicon depletion.
Therefore, studies of the silicon dissolution of biochars are
valuable means to assess the potential to use Si-rich biochars as
a novel fertilizer for silicon-depleted soil and as a powerful
remediation agent for heavy metal pollutants. The relationships
between carbon and silicon within biochars under dierent
pyrolytic temperatures are still unknown but may be related to
the carbon sequestration of biochars.
The primary objective of this study was to elucidate the
transformation, morphology, and release of silicon in Si-rich
biochars under dierent pyrolytic temperatures. To this end, a
series of biochars were produced by carbonizing rice straw
under dierent temperatures as model Si-rich biochars. Silicon
dissolution kinetics and the silicon speciation of the biochars
were evaluated by various solution extraction methods. Fourier
transform infrared spectroscopy (FTIR), X-ray diraction
(XRD), and scanning electron microscopy with energy X-ray
dispersive spectrometry (SEM-EDX) were employed to
illustrate the transformation and morphology of carbon and
silicon within biochars before and after silicon release.
MATERIALS AND METHODS
Preparation of Si-Rich Biochars. Rice straw (RS) was
selected as a precursor material of Si-rich biochars due to its
high silicon content27 and its abundance in China.32 RS was
taken from a farm near the Zijingang campus of Zhejiang
University, China. After being air-dried for 2 days and
subsequently oven-dried at 75 C overnight, RS was ground
in a grinder and then passed through a 100-mesh (0.154 mm)
sieve. The biochar was prepared by pyrolyzing rice straw under
oxygen-limited conditions under dierent temperatures. The
rice straw powder was tightly packed in a ceramic pot that was
later put in a controlled-atmosphere furnace (SSXF-4-10,
Shanghai Haoyue Instrument and Equipment CO., LTD,
China). The furnace was lled with nitrogen and was
programmed with a heating rate of 5 C min1, held for 6 h
at a specic temperature (i.e., 150 C, 250 C, 350 C, 500 C,
and 700 C), and then allowed to cool down to room
temperature naturally. The residue materials were named
RS150, RS250, RS350, RS500, and RS700, respectively, where
the sux number represents the carbonization temperature. In
addition, ash samples were produced from the rice straw by
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heating at 900 C for 6 h under air (named RS_ash). Biochars
and ash samples were then sieved to less than 0.154 mm for
subsequent analysis.
Measurement of Silicon Forms in Si-rich Biochars.
Generally, in soil, the forms of silicon can be divided into
dissolved silicon, available silicon, active silicon, amorphous
silicon, and total silicon based on dierent denitions. The
dierent forms of silicon can be measured with dierent
extraction solutions. The silicon forms in RS biochars made
under dierent temperatures and in RS_ash were measured
using similar methods. Dissolved silicon was extracted using
0.02 mol L1 CaCl2 to decrease the inaccuracy resulting from
CO32. Available silicon refers to the silicon that can be
absorbed by plants; this was extracted using the 1 mol L1
HAc-NaAc (pH = 4.0) buer method. According to
Tweneboah,33 silicon that can be easily dissolved in 0.5 mol
L1 CaCl2 at pH = 1.5 is called active silicon. Glenn et al.34
recognized that amorphous silicon could be detected by boiling
in 0.5 mol L1 NaOH for 2.5 min. For total silicon, a
gravimetric method was used. The specic steps for the
measurement of dierent silicon forms are provided in the
Supporting Information.
Dissolution Kinetics of Dissolved Silicon from Bio-
chars. The release kinetics of dissolved silicon from biochars
(RS150-RS700), rice straw biomass (RS), and RS_ash were
evaluated via two methods, i.e., batch continuous release and
repeated extraction for a given time. For continuous release
experiments, 50 mg samples were added to 50 mL plastic
centrifuge tubes with 50 mL of 0.02 mol L1 CaCl2. After
shaking at 120 rpm for dierent times (i.e., 0.25, 0.5, 1, 2, 3, 5,
7, 10, 19, 30, 40, and 60 d) at 25.0 0.5 C, the samples were
centrifuged at 1500 g for 5 min, and the supernatant silicon
concentration was detected using siliconmolybdenum blue
colorimetry. The supernatant solution pH was also monitored.
All samples were prepared in duplicate, and blank experiments
without biochar were also prepared.
Repeated extraction experiments were conducted to evaluate
potential release capacity of silicon from RS150-RS700, RS, and
RS_ash. First, 50 mg samples were mixed with 50 mL of 0.02
mol L1 CaCl2 in 50 mL plastic centrifuge tubes. After shaking
at 120 rpm and room temperature (25.0 0.5 C) for 24 h, the
samples were centrifuged at 3000 rpm (1500 g) for 5 min.
After 20 mL of the supernatant solution was removed for
silicon measurement and another 20 mL aliquot was removed
for pH measurement, the volume was replaced with 40 mL of
fresh 0.02 mol L1 CaCl2 extraction solution. After the tubes
were shaken for another 24 h, the tubes were centrifuged, and
the supernatant solution was used for silicon concentration and
pH measurements again. The repeated extraction experiment
was run until the supernatant silicon concentration was less
than 0.5 mg L1 and remained unchanged. In most samples, the
silicon concentration was below 0.5 mg L1 after 28 extractions.
The cumulative release of silicon from the samples was
calculated. Then, the samples were washed with ultrapure water
ve times to ush out CaCl2. The samples were vacuum-dried
at 60 C for 12 h and were named w-RS, w-RS150, w-RS250,
w-RS350, w-RS500, w-RS700, and w-RS_ash, respectively. The
products were stored for further analysis.
Structural Characterization of Biochars Before and
After Water Washing. The samples before and after water
washing were characterized using FTIR, XRD, and SEM-EDX.
For FTIR analysis, the samples were mixed with KBr with a 1/
100 mass ratio and then ground and pressed into lamellar form.
dx.doi.org/10.1021/es405676h | Environ. Sci. Technol. 2014, 48, 34113419
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Figure 1. FTIR spectra of rice straw (RS), rice straw-derived biochars (RS150, RS250, RS350, RS500, and RS700), and ash residues (RS_ash). The
solid lines represent the spectra of biochars before washing, and the dashed lines represent the spectra of biochars after washing (indicated with
w-).

FTIR spectra were recorded in the 4004000 cm1 region with
a resolution of 1 cm1 by a Nicolet 6700 spectrometer. For
each FTIR spectrum, 64 interferograms were collected. XRD
data were obtained at a diraction angle region of 370 by an
X-ray diractometer (RIGAKU D/MAX 2550/PC, Japan) with
CuK radiation. For SEM analysis, an SEM (FEI Quanta 3D
FEG) was operated at 20 kV with an energy X-ray dispersive
(EDX) detector to observe the biochar surface microstructure
and element distribution. The samples were polished with
platinum to ensure electrical conductivity of the surface and
were then observed under dierent magnications by SEM.
The EDX line spectra were acquired by drawing 60 m
arrows at 1000 magnication for 300 s to achieve a sucient
signal-to-noise ratio. The results were autocorrected and
optimized by Inca software.
1514 cm1 (CC), 1426 cm1 (CH2), 1159 cm1 (CO),
and 1054 cm1 (COC) were completely eliminated,
indicating the cracking of cellulose and lignin (Figure S-1).
This cracking process was also proved by Yang et al.,37 who
observed hemicellulose cracking at 220315 C and cellulose
cracking at 315400 C. Under high temperature (500700
C), only the OH (3404 cm1) and aromatic CC and C
O (1592 cm1) groups were preserved. At high temperature
ranges, the pyrogenic amorphous carbon was turned into
turbostratic crystallites.19
Typically, compared to the lower-temperature biochars, high-
temperature biochars are carbonized more completely, contain
more aromatic matter and less aliphatic matter, and show
higher aromaticity and lower polarity.3,14 The condensation and
turbostratic crystallization of carbon during the pyrolysis

RESULTS AND DISCUSSION

Carbon Transformation in Rice Straw Biochars. The
process decreases the carbon dissolution from biochars
(FigureS-2). As reported, aromatic carbon is more inert than
aliphatic carbon under biotic and abiotic oxidation con-
structural characteristics of organic matter in biochars have ditions;23 thus, the high-temperature biochars are more
been widely investigated by FTIR spectra.19 Prior studies have recalcitrant.
shown that the pyrolytic temperature plays an important role in Silicon Transformation in Rice Straw-Derived Bio-
the organic carbon structure. Figure 1 shows the FTIR spectra chars. The yields, ash contents, and total silicon contents in
of biochars, rice straw biomass, and ash residues. Abundant biochars under dierent pyrolytic temperatures are presented in
peaks for RS are found. The band at 3404 cm1 represents the Table 1. With increasing pyrolytic temperature (150 C700
OH stretching vibration. The peaks at 2909 cm1, 2852 cm1,
1426 cm1, and 1373 cm1 are assigned to CH2 groups. The Table 1. Yields, Ash Contents, Total Silicon Contents, and
band at 1640 cm1 is assigned due to CC and CO Amorphous Silicon Percentages of Rice Straw Biomass (RS),
stretching,3,26 and the band at 1514 cm1 represents the CC Biochars, and Ash Residue
stretching vibration of lignin.35 The bands at 1159 cm1 and
1054 cm1 are assigned to the alcohol CO and COC of ash content total silicon
amorphous
silicon
cellulose.35 Thermal cracking occurs in the absence of oxygen, sample a
yield (%) (%) content (%) percentage (%)
and all of these bands experience dierent changes during the RS 100 16.5 0.1 6.16 0.01 98.76 2.14
pyrolysis process. This cracking produces volatile organic RS150 93.9 0.3 13.2 0.1 4.90 0.01 101.61 1.50
matter and increases the aromatic structure content by RS250 64.6 1.9 21.0 0.1 7.79 0.01 94.77 1.23
condensation after the dehydrogenation and dehydroxylation RS350 44.0 0.4 29.3 0.0 10.87 0.01 109.33 1.98
of carbohydrates.19 Under low carbonization temperature RS500 38.7 0.4 38.3 0.1 14.21 0.01 104.58 2.33
(150250 C), most bands were preserved except for that RS700 37.0 0.2 49.2 0.2 18.29 0.02 77.62 0.61
for OH (3404 cm1), which decreased in intensity, consistent RS_ash 17.0 0.1 103.3 0.1 38.35 0.03 14.08 1.10
with the dewatering process derived from thermogravimetric
analysis (Figure S-1).36 When heated to 350 C, the peaks at a
The number represents the carbonization temperature.

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Environmental Science & Technology
C), the biochar yields decreased from 93.9% to 37.0%, ash
contents increased from 13.2% to 49.2%, and total silicon
contents increased from 4.90% to 18.29%, indicating the
accumulation of silicon components. To date, silicon trans-
formation and silicon speciation in biochar under dierent
pyrolytic temperatures have not been illustrated. In the current
study, the dierent silicon speciation forms in biochars were
initially detected by dierent extraction solutions and are
shown in Figure S-3. The nal pH value of the extraction
solution for dissolved silicon is shown in Figure S-4. The silicon
speciation and contents in rice straw-derived biochars were
signicantly aected by the pyrolytic temperatures. For a given
biochar, the speciation of silicon content (24-h extraction)
follows the order of amorphous silicon dissolved silicon >
active silicon > available silicon.
The available silicon and active silicon in biochars tend to
increase with the carbonization temperature (except for active
silicon in RS500). As for dissolved silicon, RS has a silicon-
releasing capacity of 3.69 0.10 mg g1, which rapidly
decreased with carbonization temperature (0 150 C 250
C) to 0.52 0.06 mg g1 for RS250. However, as the pyrolytic
temperature increased further (250 C 700 C), the
dissolved silicon content increased to its highest value at RS700
(7.11 0.32 mg g1). Obviously, the dissolved silicon content
in biochar is 12 orders of magnitude higher than that of
typical soil (e.g., 0.07450.980 mg g1 for the soil of Shaanxi
province and the recommended silicon content of 0.095 mg g1
in China38,39). Although the RS_ash sample contained
extremely high total silicon content, the dissolved silicon in
the sample was very low. The amorphous silicon content
increased with the carbonization temperature. After normal-
ization by the total silicon (Table 1), interestingly, all the
amorphous silicon percentages were approximately 100%
except for those for RS700 (77.64%) and RS_ash (14.08%)
(Table 1), suggesting that the silicon in the biochars (RS150-
RS500) and RS biomass were amorphous silicon. The crystal
silicon contents in RS700 and RS_ash were approximately
22.36% and 85.92%, respectively.
The silicon transformation in biochars was supported by
FTIR (Figure 1) and XRD (Figure 2). FTIR spectra displayed
Figure 2. XRD spectra of derived biochars and ash residues before and
after water washing. RS250, RS350, RS500, and RS700 refer to
biochars; w-RS250, w-RS350, w-RS500, and w-RS700 refer to washed
biochars. RS_ash and w-RS_ash refer to ashes before and after
washing. (Sy: sylvite, Go: gonnardite, Q: quartz, Cr: cristobalite, Tr:
tridymite, Ca: calcite).
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silicon-containing group vibration absorptions at 1200 cm1,
1092 cm1, 897 cm1, 788 cm1, and 471 cm1. Peaks at 1092
cm1, 788 cm1, and 471 cm1 that are assigned to the SiO
Si group became sharper with increasing pyrolytic temperature.
In particular, the 1200 cm1 peak (or shoulder) assigned to
disordered silicon40 became less intense and even disappeared
with increasing pyrolytic temperature, implying the formation
of silicon crystal at high temperature.29 Furthermore, XRD data
(Figure 2) conrmed the presence of some silicon crystal
(mainly in the form of quartz) in RS350 and RS700. Due to
being obscured by amorphous carbon peaks, no silicon crystal
peak was observed in RS500. Ash residues contained a large
quantity of crystalline silicon (mainly cristobalite, tridymite, and
quartz).
The silicon in rice straw biomass includes silicic acid and
polymeric silicic acid.41 When rice straw is converted into
biochar, the silicon speciation and silicon release capacity
drastically change during the carbonization process. The
dissolution of silicon would have a potential eect on the
available silicon content of soil because biochar has been
suggested for use as a soil amendment and may act as a novel
silicon source due to its high dissolved silicon content. The
amount of released silicon is dependent on silicon speciation,
which can be regulated by the pyrolytic temperature. To the
best of our knowledge, this is the rst report on the
transformation of silicon in rice straw-derived biochars under
dierent pyrolytic temperatures. Long-term silicon release from
biochars is illustrated by dissolution kinetics experiments in the
following sections.
Silicon Dissolution Kinetics of Rice Straw-Derived
Biochars. The long-term silicon dissolution of biochars is
highly related to the amount of silicon available for release into
the soil. Time-dependent silicon dissolution kinetics data are
presented in Figure 3, and the corresponding pH values are
shown in Figure S-5. In the rst 12 h, RS150, RS250, RS350,
and RS_ash exhibited a relatively slow silicon dissolution rate,
while RS, RS500, and RS700 displayed a relatively fast silicon
dissolution rate. For RS, the amount of released silicon was
close to that of RS700 at 12 h. The amount of released silicon
at 1 day followed the order of RS700 > RS500 > RS > RS350 >
RS150 RS_ash > RS250, which is in accordance with the
dissolved silicon quantities shown in Figure S-3a.
Based on Figure 3, the long-term release of silicon from the
tested samples was divided into three groups. For RS, RS150,
and RS250, the released silicon linearly increased with the
reaction time, and their time-dependent release curves almost
overlapped. For higher temperature biochars (RS350, RS500,
and RS700), the released silicon nonlinearly and sharply
increased with the dissolution time; silicon dissolution kinetics
at 130 d were similar, while at 3060 d, dierent silicon
dissolution behaviors were observed. For the RS_ash sample,
the released silicon was at a minimum, and silicon release was
unchanged with reaction time. Therefore, silicon release
behavior is controlled by the silicon speciation and content as
well as by the interaction of silicon and carbon. The
corresponding pH values of the dissolution kinetics in Figure
S-5 were a little variable over the rst ten days, and then
relatively stable pH values appeared, increasing with pyrolytic
temperature. The solution pH may be another important factor
that inuences silicon dissolution from biochars.
To eliminate the inuence of pH on silicon release, repeated
extraction by fresh solution was conducted to monitor the
silicon dissolution kinetics. The extraction solution pH value
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Environmental Science & Technology
Figure 3. Silicon-dissolving kinetics of RS, derived biochars (RS150, RS250, RS350, RS500, and RS700) and ash residues (RS_ash). The solid to
liquid ratio is 50 mg/50 mL. The corresponding pH values in extraction solution are shown in Figure S-5.
was kept at 6.58 0.12 after the rst ve extractions (Figure S-
6). The cumulative silicon dissolution amount is displayed in
Figure 4. The daily dissolution amount can roughly be regarded
Figure 4. Cumulative silicon dissolution of RS, derived biochars
(RS150, RS250, RS350, RS500, and RS700) and ash residues
(RS_ash). The solid to liquid ratio is 50 mg/50 mL. Because the
pH is stable at 6.58 0.12 after 5 days (Figure S-6), the pH eect on
dissolution is negligible.
as the dissolving rate. Hence, the rst days silicon dissolving
amount represents the initial dissolving rate, which is in line
with the kinetics results of the batch continuous release
experiments. The initial dissolution rate of silicon was in the
order of RS700 > RS500 > RS > RS350 > RS150 > RS250,
suggesting that the initial dissolving rate decreased at rst and
then rose with pyrolysis temperature. This phenomenon may
be partly explained by the dierence in pH values in the
extraction solution. Higher pH leads to a higher dissolving rate.
As the pyrolysis temperature increases, the pH also increases
(Figure S-6), thus resulting in an increased silicon dissolving
rate after 250 C. However, the low silicon release for RS,
RS150, and RS250 may be attributed to other reasons (such as
structure and silicon speciation). Although the pH eect was
ruled out after ve days, the cumulative silicon dissolving curves
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still depended on the pyrolysis temperature. RS showed a slow
silicon dissolving rate for the rst 10 days but then showed a
quadratic increase of cumulative silicon dissolution. A similar
trend was found in RS150 but with a shorter period of slow
silicon dissolution. RS250 showed a linear curve for cumulative
silicon dissolution. RS350, RS500, and RS700 all showed a
quadratic increase.
Figure 4 displays the changed trend of the nal cumulative
silicon dissolution order after the 28-day extraction (red
arrows).This order would be magnied if adjusted by the total
silicon content in biochars (data not shown). Based in Figure 4,
the decrease in silicon release from RS to RS250 is possibly
caused by the gradual elevation of the compacted structure of
carbon components, which has also been suspected as the
reason for the slow sorption rate.26 The drastic change in the
silicon release from RS250 to RS350 was attributed to the
cracking of organic components, causing the exposure of the
silicon components. The decreased silicon dissolution from
RS350 to RS700 may be associated with the amorphous silicon
content within biochars because the nal cumulative released
silicon quantity at 28 days reects the potential capacity of
silicon release and amorphous silicon is more soluble than
crystal silicon. As shown in Table 1, the amorphous silicon
percentage for RS350, RS500, and RS700 decreases with the
pyrolysis temperature. In other words, the silicon dissolving
rate and quantity are tightly connected to the pyrolysis
temperature, which leads to variations in pH, structure, silicon
form, and other properties.
The results of kinetic and continuous extraction experiments
suggest that silicon dissolution is aected by many factors such
as pH value, silicon form, biochar structure, and others. To
determine the other factors that may inuence silicon
dissolution, the biochars before and after washing were
monitored by XRD (Figure 2) and SEM-EDX (Figure 5).
These two silicon dissolution experiments show large and long-
term silicon dissolution from RS biochars, implying a large
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Figure 5. SEM-EDX images of RS and biochars (RS250, RS350, RS500, and RS700) before and after washing. The bold red arrow shows the line-
scan path.

Figure 6. Schematic illustration of the carbonsilicon structural interaction, along with the variations in carbon and silicon form caused by the
biochar preparation temperature. The numbers after RS represent the carbonization temperatures.

application potential in agriculture in order to improve the
available silicon content in soils.
The CarbonSilicon Interaction within Biochars and
Its Eect on Dissolution. The morphologies of carbon and
silicon colocated in RS biochars under dierent temperatures
were monitored by SEM-EDX (Figure 5). The line-scan was
used to analyze the supercial elemental composition.
Compared to mapping, line-scans give a visual picture that
can reect the relative elemental content. Noting that the
3416
relative intensity of dierent elements does not directly indicate
the elemental content, we set RS as the contrast material. By
comparing with RS, the qualitative carbon, silicon, and oxygen
contents on the surface of biochar could be analyzed. For RS,
the main elements detected on the surface were carbon, silicon,
and oxygen, and their signals overlapped. The oxygen line-scan
signal decreased with the pyrolysis temperature (RS RS250
RS350), reaching almost zero for RS500 and RS700, which
is in accordance with the charring processes described with TG-
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Environmental Science & Technology
DTG (Figure S-1). The carbon line-scan signal relative to
silicon seemed to increase for RS250 and RS350 due to the
decreased oxygen during the pyrolysis period and then
decreased for RS500 and RS700 due to the loss of carbon.
Taking the washing process into account, we found a silicon-
predominant surface for w-RS250 and a carbon-predominant
surface for w-RS700. The surfaces of w-RS350 and w-RS500
seem to represent a transitional state between w-RS250 and w-
RS700. It is easy to deduce that the carbon (or silicon) in the
surface was swept away during washing by comparing w-RS250
with RS250 (or w-RS700 with RS700).
As proposed by Ma and Takahashi,41 Si-containing
compounds are deposited in dierent tissues of rice, and the
special cuticle wax silica layer is located in the rice leaf.42,43
Therefore, we put forward a CSi structural model for rice
straw biochars, which is presented in Figure 6. In this model,
for RS, the outermost layer (C1) is a cuticle layer that mainly
contains carbon, the inner layer (Si) is a silicon layer, and the
innermost (C2) is carbon again. The color of the C1 and
C2 layers changes from orange to dark with increasing
preparation temperature, indicating the change in carbon form.
The biochar changes identied with SEM-EDX strongly
support the carbonsilicon structural interaction model. To
be specic, the silicon-predominant surface for w-RS250 was
caused by water that ushed out the cracking C1 layer and
thus exposed the Si layer. As for w-RS700, both theC1 and
Si layers were swept away by water, and thus the innermost
C2 layer was exposed.
Using the carbonsilicon interaction model (Figure 6), the
distinct silicon dissolution characteristics in dierent biochars
may easily be illustrated. Silicon dissolution is controlled by the
cointeraction of the silicon location, content, and form. In RS,
the free water inside dissolves silicic acid and the C1 layer is
loose, which results in a high quantity of dissolved silicon
(Figure S-3a) and a relatively fast dissolution rate (Figure 3).
The Si dissolution rate increases after an eight-day slow period
(Figure 4) because the dissolution of organic matter from the
C1 layer promotes silicon dissolution. RS150 is similar to RS,
but dehydration makes RS150 more compact and free from
silicic acid polymerization, which leads to a low quantity of
dissolved silicon in comparison with RS (Figure 4). The
structural dierence between RS250 and RS150 is that RS250
starts to pyrolyze (Figure S-1), but the more compact structure
and the polymerization of silicic acid in RS250 results in the
lowest silicon dissolution quantity (Figure 4). Interestingly, in
RS350, carbon cracking makes the C1 layer tatter, and then
the Si layer is exposed (Figure 6), bringing about the largest
silicon dissolution among the tested biochars (Figure 4). As the
pyrolysis temperature increases to 500 C, the exposed silicon
(Figure 5) and the initial dissolving rate in RS500 become
greater. However, due to the formation of silicon crystal, the
nal cumulative silicon dissolution quantity is less than RS350.
In RS700, the charring process increases the exposure of silicon
to water, which is shown in Figure 5, but the crystal process
limits the nal cumulative silicon dissolution quantity (Figure
4).
The variations in carbon and silicon form in biochars result
in the mutual protection between carbon and silicon under
dierent preparation temperatures (Figure 6). In brief,
dehydration results in a more compact structure so that the
silicon in biochars becomes dicult to dissolve, reecting the
protection of silicon by carbon. The pyrolysis of organic matter
exposes the silicon to the solution, leading to fast and extensive
3417
Article
silicon dissolution. As the carbon chars, the silicon crystallizes,
which results in a slightly decreased total silicon dissolution.
These two processes reect the protection of carbon by silicon.
Overall, the protective interaction between carbon and silicon is
the comprehensive result of the structures and morphologies of
the carbon and silicon components. The protective interaction
between carbon and silicon within biochar particles strongly
inuences silicon dissolution, further determining the applica-
tion of biochars as silicon fertilizers in agriculture. On the other
hand, this interaction may also dominate carbon stability within
biochars, including its bioavailability, sorption, and dissolution.
Environmental Implications. Increasing attention has
been focused on the use of biochars as soil additives in
agriculture. Biochars have proved to be valuable in a variety of
processes that use them as the N, P, and K nutrient sources.44
Furthermore, biochars impact the biogeochemical cycling of
carbon, nitrogen, and phosphorus.4547 However, the silicon
content in silicon-rich biochars, which is generally neglected,
has not raised concerns. The testing of silicon dissolution and
the discovery of carbonsilicon protective interactions in the
current study indicate the importance of silicon in biochars.
Therefore, more studies are needed to examine the silicon-
fertilizing potential of biochar and its eect on silicon transport
from the land ecosystem to the sea ecosystem; large amounts of
arable land (including those in China48) are actually silicon
depleted, and Si-rich biochar may create a potentially large pool
of reactive biogenic silica49 in the silicon geochemical cycle. On
the other hand, biochar is considered to be a carbon-
sequestering material; the protective interaction between
carbon and silicon is essential to its stability, and silicon release
is a part of the aging process of biochars. Moreover, the
dissolution of silicon from biochar in the soil may inuence the
sequestration of atmospheric carbon dioxide.50 Further studies
should focus on inorganic matter in biochars, especially
components such as silicon whose morphology may change
during biochar preparation.
*
ASSOCIATED CONTENT
S Supporting Information
The measurements of dierent silicon forms in biochar are
presented here. The TG-DTG curves of rice straw biomass are
presented in Figure S-1, the dissolved carbon quantity of
biochars is presented in Figure S-2, the silicon forms content
within biochars is presented in Figure S-3, the nal pH in
extraction solution is presented in Figure S-4, the pH variation
corresponding with silicon dissolution kinetics is presented in
Figure S-5, and the daily pH of the continuous extraction
experiments is presented in Figure S-6. This material is available
free of charge via the Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Phone: 0086-571-88982587. Fax: 0086-571-88982587. E-mail:
blchen@zju.edu.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This project was supported by the National Basic Research
Program of China (Grants 2014CB441106), the National
Natural Science Foundation of China (Grants 21277120,
dx.doi.org/10.1021/es405676h | Environ. Sci. Technol. 2014, 48, 34113419
Environmental Science & Technology
21137003, 41071210), and the Doctoral Fund of Ministry of
Education China (Grant J20130039).
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