b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

Available online at www.sciencedirect.com

http://www.elsevier.com/locate/biombioe

Chemical characterization of rice straw-derived biochar for

soil amendment
Weixiang Wu a,*, Min Yang a, Qibo Feng a, Kim McGrouther b, Hailong Wang b,c,
Haohao Lu a, Yingxu Chen a
a

Ministry of Agriculture Key Laboratory of Non-point Source Pollution Control, Institute of Environmental Science and Technology,
Zhejiang University, 866 Yuhangtang Road, Hangzhou 310058, PR China
b
Scion, Private Bag 3020, Rotorua 3046, New Zealand
c
School of Environmental and Resource Sciences, Zhejiang A & F University, Linan, Hangzhou 311300, PR China

article info

abstract

Article history:

Pyrolysis of rice straw to create biochar for soil amendment appears to be a promising

Received 16 December 2011

method to address concerns with regard to improving soil fertility, increasing Carbon

Received in revised form

storage and decreasing Green House Gas emissions. However, the ability of rice straw-

15 June 2012

derived biochar to affect these factors might vary depending on its characteristics. It is

Accepted 12 September 2012

therefore essential to investigate the properties before large-scale application of rice straw-

Available online 6 October 2012

derived biochar. In this study, rice straw-derived biochars produced at different temperatures (300, 400, 500, 600 & 700
C) and residence time (1, 2, 3 & 5 h) were characterized

Keywords:

using a suite of analytical techniques. Results showed that pyrolysis temperature had

Rice straw

a greater influence than residence time on the chemical composition and structure of rice

Characterization

straw-derived biochar produced at low heating rate. The rice straw-derived biochars

Biochar

especially produced at 400
C had high alkalinity and cation exchange capacity, and high

Pyrolysis condition

levels of available phosphorus and extractable cations. These properties indicate potential

Stability

application of rice straw-derived biochar as a fertilizer and soil amendment. Fourier

transform infrared spectra showed that higher pyrolysis temperatures promote condensation reactions. Rice straw-derived biochars contained turbostratic crystallites at 400
C,
and displayed a high level of aromatization at 500
C. Increasing charring temperature will
increase the aromaticity of biochar, and might include its recalcitrance.
2012 Elsevier Ltd. All rights reserved.

1.

Introduction

China, with a long history of agricultural development,

currently faces an urgent problem of significant carbon (C)
loss from agricultural paddy soils due to the intensive cropping system used for food production. Direct incorporation of
rice straw into paddy soil has long been promoted by the
Chinese government to conserve soil nutrients and organic
carbon content. Although this management practice helps to
improve soil fertility, it only results in a slight increase in soil

organic carbon and in the process creates significant increase

in methane (CH4) released to the atmosphere [1]. Formation of
rice straw-derived (RSD) biochar appears to be a promising
method to address the problem of reductions in soil nutrients
and C storage, and increased Green House Gases (GHGs)
emissions associated with rice straw application from rice
paddies [2,3].
Generally speaking, biochar is more stable relative to other
soil organic matter forms [4]. According to laboratory incubation and field observation, it is estimated that biochar could

* Corresponding author. Tel./fax: 86 571 88982020.

E-mail address: weixiang@zju.edu.cn (W. Wu).
0961-9534/$ e see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.biombioe.2012.09.034

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

persist in soil for hundreds to thousands of years [5,6]. Hence,

carbonizing biomass with biochar application to soil may
proactively sequester C from the atmosphere through photosynthesis. In addition, it is believed that application of biochar
to soil is a potential approach for reducing CH4 and nitrous
oxide (N2O) emissions from soil [7e9], especially for rice paddy
soil which is a significant source of GHGs in China [10].
Moreover, the long-term benefits of biochar application
potentially include increased adsorption ability, reduced loss
of nutrients via leaching and increased soil organic carbon;
thus improving soil fertility [11e15].
However, the actual environmental function of biochar in
soil had been shown to vary depending on the physical and
chemical characteristics of the biochar. Through laboratory
incubation of biochar in sandy loam soil, Bruun [16] found that
1.9% and 1.4% of barley charcoal produced at 225
C and 300
C
had been evolved as CO2 during first 30 days, which indicated
that mineralization decreased with increasing production
temperature. The degree to which CH4 and CO2 emissions can
be reduced has been shown to vary depending on the feedstock used to produce biochar [9]. Biochar derived under
different pyrolysis temperature could have different sorption
mechanisms. Through sorbing benzene and nitrobenzene,
Chun et al. [17] reported that sorption by high-temperature
chars occurred almost exclusively by surface adsorption,
whereas the sorption by low-temperature chars occurred via
surface adsorption and, to a lesser degree, partitioning into
the residual organic-matter phase. The large negative surface
charge of biochar could directly retain positively charged
nutrients and decrease nutrients leaching [18]. But none of
sorption mechanisms are reported relevant to the effect of
biochar on GHGs reduction. Depending on charring temperature and feedstock, as a liming material for overcoming soil
acidity and a direct source of nutrients, biochar also has the
potential to alter soil solution chemistry and therefore influence the growth of plants [19,20]. Although it is clear that the
behaviour of biochar in soil is related to the characteristics
created during the pyrolysis process, RSD biochar has received
little attention to link its behaviour in the agro-ecosystem to
its chemical properties [21]. Thus, it is important to examine
the properties of RSD biochar created over a range of
temperatures and residence times and to relate these variables to its function in paddy soil.
The objective of this study was to determine the effect of
pyrolysis temperature and residence time on the chemical
composition and structure of RSD biochar. In order to achieve
this objective, we carbonized rice straw at five temperatures
(300, 400, 500, 600 & 700
C) and four residence times (1, 2, 3 &
5 h). Biochar characterization included chemical tests,
elemental and proximate analysis, X-ray Diffraction (XRD),
Fourier transform infrared (FTIR) spectroscopy and Solid-State
13
C Nuclear Magnetic Resonance (NMR) spectroscopy.

2.

Methods

2.1.

Biochar production

Rice straw (Oryza sativa) was collected from a paddy field in

a suburb of Hangzhou (119.5
E, 30.2
N), Zhejiang province,

269

China. It contained 422.0 g/kg C, 9.9 g/kg N, 1.2 g/kg P, 12.1 g/kg
K, 6.5 g/kg Ca, 1.4 g/kg Na and 1.6 g/kg Mg. Before charring, the
rice straw was dried at 60
C for 24 h to <10% moisture and cut
to a particle size of 2 cm. For pyrolysis, the samples were
placed in a GDL-1500X tubular furnace (Kejin, Hefei, China)
equipped with a corundum tube (32 mm diameter  700 mm
length) with a N2 purge (1 L/min flow rate) to ensure an
oxygen-free atmosphere. Heat treatments were performed in
temperatures of 300, 400, 500, 600 and 700
C, respectively. The
heating rate was 5
C min1. Each temperature was maintained for 1, 2, 3 or 5 h before cooling to ambient temperature
under N2 flow. The char yield was recorded and the biochar
samples were milled to pass a 0.25 mm sieve (60 mesh) prior to
further analyses. Samples are hereafter referred to as TeR,
with T and R indicating the final charring temperature
(300e700
C) and residence time (1, 2, 3 & 5 h), respectively.

2.2.

Characterization

The biochars produced were subjected to the following

procedures. Proximate analyses were conducted according to
the American Society for Testing and Materials (ASTM) D176284 [22] to determine volatile matter (VM), ash content and
fixed C. Total carbon, nitrogen, and hydrogen were measured
on a LECO-CHNS932 (USA), and oxygen content was determined by difference, assuming biochar to be composed of C,
N, H, and O only. All of them were on an ash-free basis. The pH
in water and 1 M KCl solution was measured at 1:20 (w/v) ratio
after occasionally stirring over 1 h [23]. The surface acidity and
alkalinity were measured by base adsorption and acid
adsorption, respectively [24,25]. The base or acid uptake of
biochar was converted to the content of surface acidity or
surface basicity (cmol kg1), respectively. Extractable cations
(K, Ca2, Na, Mg2) and the cation exchange capacity (CEC)
of the original untreated biochar samples were measured
using 1 M ammonium acetate (pH 7) methods [26]. Available
phosphorus (P) was extracted by placing 1 g of biochar in
20 mL of 0.5 M NaHCO3 for 30 min. Extracts were then filtered
and analysed using the molybdate method [27].

2.3.

FTIR

FTIR absorbance spectra were recorded on a Shimadzu

IRPrestige-21 at wave numbers from 400 to 4000 cm1. Biochar
which had been milled to pass a 0.25 mm sieve was transferred into an agate mortar and finely ground, then KBr was
added, mixed and ground to a fine power to prepare a KBr
pellet. KBr pellets were prepared containing 0.1 wt% of finely
ground biochar powder. One hundred scans were averaged
with a resolution of 4 cm1 by subtracting values obtained
from pure KBr pellets. Carbon chemical functional groups
were assigned to wave numbers from FTIR spectra as follows:
3600e3200 cm1 to OeH stretching of hydroxyl groups;
2950e2850 cm1 to CeH stretching of aliphatic CHx,
1740e1700 cm1 to C]O stretching of carboxyl and ketones,
1630e1600 cm1 to C]C stretching of aromatic components
and to a smaller extent to C]O stretching in quinones and
ketonic acids, 1440 cm1 to C]C stretching of aromatic C,
1375 cm1 to aliphatic deformation of CH2 or CH3 groups or
OeH bending of phenoliceOH, and 1110e1030 cm1 to CeOeC

270

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

stretching vibrations in cellulose and hemicellulose;

900e750 cm1 to CeH bending aromatic CH out-of-plane
deformation.

2.4.

XRD

A traditional powder X-ray diffraction method was used to

determine the atomic structure of the biochars. Diffraction
patterns were recorded on a PANalytical XPert Pro (Holand)
instrument equipped with copper Ka radiation (30 kV, 30 mA)
as the X-ray source. Samples were packed into an aluminum
holder and all scans were recorded over the 2q range of 5e80

using a step size of 0.01
and a scan speed of 10 s/step.

2.5.

NMR

Solid-state 13C NMR measurement was conducted using

a Bruker AVANCE Z 400WB spectrometer (Bruker BioSpin AG,
Switzerland) at 100 MHz for RSD biochar produced at 400 and
500
C for 3 h. The high-speed Cross Polarization (CP) 13C NMR
experiment was run using a Bruker 4-mm double-resonance
probehead. According to Brewer et al. [28], qualitative biochar composition information, in particular alkyl carbon
composition, was obtained with good sensitivity by 13C CP/
TOSS NMR experiments with samples in 4-mm rotors at
a spinning speed of 8 kHz, a contact time of 500 ms, a 1H 90

pulse length of 2.7 ms and a recycle delay of 0.5 s to make sure
that all carbon sites will be relaxed to <5% within the recycle
delay. Four pulse TOSS was employed before detection and
spinal64 decoupling was applied for optimum resolution.
Quantitative 13C Direct Polarization/Magic Angle Spinning
(DP/MAS) NMR experiments were performed using 4-mm

sample rotors at a spinning frequency of 14 kHz. The pulse

program aringdec (anti-ring with decoupling) was applied to
suppress deadtime and background signals, the 13C 90
pulse
length was 4.5 ms and a TMMP15 decoupling pulse program
was used. All spectra were calibrated using the methine
carbon atoms of adamantane as an external standard
(d 29.47 ppm).

3.

Results and discussion

3.1.

Chemical composition of RSD biochar

The chemical properties of the rice straw-derived biochars

over a range of temperature and residence time are shown in
Tables 1,2. Yield and volatile content of the biochar decreased
with increasing temperature from 49% and 37% to 35% and
13%, respectively. Fixed C and ash content increased with
increasing temperature. The most remarkable changes in
yield, VM, fixed-C and ash contents of the RSD biochar were
observed at temperatures between 300
C and 400
C. Variations in yield and results for proximate analyses of the chars
obtained with increasing temperature were in accordance
with well-known general trends [29]. In contrast to fescue
straw biochar yields at temperatures reported by Keiluweit
et al. [30], the RSD biochar in this study showed lower yield at
300
C and higher yield over 400
C. The biphasic model of
biochar degradation shows that biochar contain two pools:
the labile and stable fraction [31]. VM gave relative measures
of the labile components of biochar. Considering a rapid decay
of the labile fraction and co-metabolism could be caused by
labile compound intrinsic to the biochar, the decrease of VM

Table 1 e Yield, proximate and elemental analysis of rice straw-derived (RSD) biochars.
Component,a wt%

Sample ID
Yield
300-1
300-2
300-3
300-5
400-1
400-2
400-3
400-5
500-1
500-2
500-3
500-5
600-1
600-2
600-3
600-5
700-1
700-2
700-3
700-5

49.5
50.1
49.8
49.1
42.8
42.3
41.1
42.0
39.0
38.6
38.0
38.6
35.7
35.1
36.1
36.3
34.7
33.5
35.2
36.5

VM
40.2
38.4
35.4
35.8
25.2
25.8
26.6
24.5
23.3
20.7
18.9
19.4
14.9
13.2
14.3
13.1
13.8
14.9
11.7
13.1






















1.4
1.6
1.2
2.0
1.2
1.0
0.7
0.9
3.5
0.4
1.0
2.4
3.2
1.9
0.1
0.0
1.6
3.0
0.1
4.0

Ash
22.9
25.4
24.2
24.4
28.8
27.6
29.1
29.2
31.8
30.1
31.0
33.0
27.6
28.4
32.6
33.2
29.3
28.2
34.7
34.1






















1.0
0.9
0.3
0.2
0.3
0.3
0.2
0.6
0.5
0.2
0.6
1.3
0.6
0.3
1.0
0.9
0.0
0.0
0.7
0.4

Atomic ratio

Fixed C

H/C

O/C

36.9
36.2
40.3
39.7
46.0
46.6
44.3
46.4
44.9
49.2
50.1
47.5
57.5
58.3
53.1
53.7
56.8
56.9
53.6
52.8

72.1
72.5
74.7
74.4
77.2
77.0
81.4
80.5
82.8
82.6
84.7
83.8
87.1
83.6
88.7
88.7
90.6
90.6
87.4
85.2

5.03
5.13
5.09
4.87
4.01
3.99
4.19
3.97
3.25
3.28
3.54
3.09
2.51
2.46
2.39
2.20
1.80
1.79
2.00
1.61

1.55
1.76
1.72
1.72
1.74
1.80
1.77
1.86
1.77
1.76
1.73
1.82
1.52
1.46
1.66
1.55
1.41
1.34
1.58
1.60

21.3
20.7
18.5
19.0
17.0
17.2
12.6
13.6
12.1
12.3
10.1
11.3
8.8
12.5
7.3
7.6
6.2
6.3
9.1
11.6

0.84
0.85
0.82
0.79
0.62
0.62
0.62
0.59
0.47
0.48
0.50
0.44
0.35
0.35
0.32
0.30
0.24
0.24
0.27
0.23

0.22
0.21
0.19
0.19
0.17
0.17
0.12
0.13
0.11
0.11
0.09
0.10
0.08
0.11
0.06
0.06
0.05
0.05
0.08
0.10

a Yield and VM (volatile matter), ash, fixed C are on a water-free basis (dried at 105
C). Elemental contents and atomic ratios are on a dry ashfree basis.
b Shown are average value from two replicate measurements  standard deviations.

271

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

Table 2 e pH, surface acidity and alkalinity, cation exchange capacity (CEC) and extractable cations in RSD biochars. Values
are given as mean standard deviation for duplicate measurements.

300-1
300-2
300-3
300-5
400-1
400-2
400-3
400-5
500-1
500-2
500-3
500-5
600-1
600-2
600-3
600-5
700-1
700-2
700-3
700-5

pH
H2O

KCl

9.19  0.03
9.31  0.01
9.24  0.07
9.28  0.01
9.96  0.04
9.58  0.03
10.62  0.04
10.10  0.07
10.48  0.04
10.45  0.01
10.89  0.03
10.67  0.01
10.84  0.02
10.91  0.02
11.03  0.01
10.88  0.14
10.77  0.01
10.77  0.06
11.20  0.08
10.87  0.03

8.45  0.07
8.55  0.04
8.56  0.08
8.55  0.08
9.34  0.01
9.04  0.01
10.02  0.03
9.59  0.01
10.04  0.01
10.00  0.01
10.55  0.01
10.24  0.00
10.43  0.01
10.53  0.00
10.78  0.07
10.59  0.01
10.56  0.01
10.51  0.06
10.92  0.06
10.15  0.01

Surface
acidity
(cmol/kg)

Surface
alkalinity
(cmol/kg)

P (mg/kg)

 4.3
 4.3
 2.1
 2.8
 2.2
 5.8
 0.7
 10.1
 2.8
 2.1
 5.6
 7.1
 2.1
 3.6
 0.0
 4.3
 6.6
 0.7
 6.5
 6.6

83.6  1.4
95.6  2.1
97.7  9.2
93.6  1.4
125.7  4.3
132.2  1.4
138.6  1.4
142.0  0.7
152.4  1.5
147.3  0.7
141.4  1.4
151.8  6.5
125.2  3.6
126.9  2.2
154.3  6.5
151.4  4.4
147.0  2.9
122.7  0.7
147.2  2.9
147.3  2.9

376.6  19.8
388.1  71.6
392.1  16.9
377.3  3.2
847.1  72.8
923.0  58.2
784.7  0.7
767.7  5.9
595.9  27.7
677.2  54.7
551.0  14.1
799.8  71.3
293.8  6.1
246.4  1.0
272.6  8.3
342.4  3.3
180.5  8.0
173.2  5.9
191.4  4.6
138.2  23.6

184.2
183.7
186.5
179.8
118.8
122.7
104.9
99.5
46.0
60.7
49.6
48.4
43.3
54.0
42.0
37.8
45.6
52.9
45.8
49.6

with increasing pyrolysis temperature might show that the

higher the producing temperature the higher the stability. The
ash content of rice straw biochar was higher than that derived
from grass (<20%) and woody feedstock (typically lies between
2 and 8%) [30]. This result might be ascribed to high ash
content (especially Si) of rice straw compared to wood, grass
or other crop residues [32]. Rice straw could be ideally applied
to biochar production as the high ash content can provide
additional fertilizer effects.
Elemental analysis indicated that C content increased,
while H and O decreased with increasing charring temperature, resulting in the progressive decrease of H/C and O/C
ratios in the RSD biochars. N content increased from 300
C to
400
C, but decreased afterwards. The changes of elemental
concentrations in RSD biochar with increasing charring
temperature were consistent with previous observations by
Keiluweit et al. [30] for pine shavings, fescue straw; and by
Bonelli et al. [33] for shells of peanuts and hazelnuts. The
decrease in H/C and O/C ratio with charring temperature was
due to the progressive dehydration and decarboxylation
reactions and indicative of the formation of structures containing condensed carbons such as the aromatic rings inferred
from FTIR spectra (1600, 1038 cm1). This inference was well
supported by the van Krevelen diagram (Fig. 1), which clearly
showed highly condensed components formed at higher
temperatures. Although the general trends in elemental
composition were consistent, the magnitude of the changes
observed varied from different studies. When pyrolysed at the
same temperature and residence time, the yield, C and N
contents of RSD biochars were much higher than those reported by Peng et al. [21] with a similar starting material (rice
straw), while ash content to the contrary. Such variations
might be a function of the differences in process condition, such as pyrolysis technology, heating rate and the

CEC
(cmol/kg)
56.9
60.6
59.2
58.7
61.6
63.9
57.1
46.1
32.0
26.9
23.6
31.2
23.9
19.0
20.2
23.0
23.1
23.1
24.5
22.7

 3.1
 3.9
 3.0
 0.0
 3.4
 0.0
 3.9
 1.9
 1.2
 2.8
 1.0
 4.6
 3.5
 0.5
 1.0
 5.3
 5.8
 2.4
 4.0
 0.9

Extractable cations (cmol/kg)

K

Ca

47.8  2.0
49.6  2.1
51.5  1.9
46.5  5.7
61.3  7.0
55.1  3.3
56.2  2.2
61.4  3.1
57.0  1.0
54.3  1.5
55.7  2.1
55.9  1.7
47.9  5.3
46.5  3.7
60.8  1.1
55.2  5.0
46.7  0.5
36.6  0.3
49.9  2.3
48.2  0.0

7.1
7.9
7.8
7.4
12.2
11.9
11.7
13.4
12.0
12.0
9.9
9.7
8.0
7.9
11.2
9.0
7.8
6.1
8.8
8.5

 0.3
 0.4
 0.3
 0.6
 1.2
 0.6
 0.4
 0.3
 0.1
 0.2
 0.5
 0.1
 0.8
 0.6
 0.1
 0.6
 0.0
 0.1
 0.7
 1.8

Mg

Na

3.4  0.1
3.5  0.2
3.5  0.1
3.1  0.3
4.1  0.4
3.8  0.2
3.6  0.2
3.9  0.1
2.5  0.0
2.4  0.0
2.0  0.1
2.1  0.0
1.7  0.2
1.3  0.1
2.3  0.0
2.0  0.2
1.7  0.0
1.2  0.0
2.2  0.2
2.2  0.0

6.6  0.3
7.0  0.2
7.8  0.1
6.7  0.8
8.5  1.1
8.1  0.5
7.7  0.5
8.8  0.8
8.2  0.0
7.4  0.3
6.7  0.3
6.4  0.3
5.3  0.7
5.1  0.5
8.2  0.2
6.6  0.5
5.8  0.1
3.8  0.2
6.5  0.5
5.7  0.0

degree to which O2 was excluded from the samples during

heating [34].
Contrary to the changes of surface acidity, pH and surface
basicity increased with the charring temperature, although
some fluctuation could be found with charring residence time.
The effects of charring temperature on available K, Ca, Na and
Mg corresponded to that seen with CEC. CEC, available P,
extractable cations (K, Ca2, Na, Mg2) and N content
increased from 300
C and reached their maximum values at
400
C. The trend of pH with increasing temperature was
consistent with that of ash content. It is supported by salts of
alkali and alkaline elements (Na, K, Ca, Mg) and calcite which
are the main component of ash [20]. The change of N indicates
that N enriched first, and then lost via volatilisation during
pyrolysis with increasing temperature. While the decrease of
available P and CEC might be due to reduction of the availability of P and cations. Shinogo has reported that the
1.0
300

400

500

600

700

0.8
0.6
H/C

Sample
ID

0.4
0.2
0.0
0.0

0.1

0.2
O/C

0.3

0.4

0.5

Fig. 1 e Van Krevelen plot of elemental ratios for RSD

biochars.

272

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

3.2.

FTIR of RSD biochar

Changes in FTIR spectral properties of RSD biochars over the

range of charring temperatures and residences time are presented in Fig. 2. The FTIR spectra of rice straw was similar to
that of cellulose [44,45]. During carbonization, the carbonized
components lead to the increasing upward drift in baseline at
high wave number which is assigned to low-energy electron
excitations of condensed aromatic structures [46,47]. Biochar
derived from biomass can experience several phase transitions [30,48] and the RSD biochar studied here followed
a similar trend.
At 300
C, the loss of aliphatic CeH stretching (2950 and
2850 cm1) and CeO stretching (1110e1030 cm1) and lower H/

O-H

C-O-C
C=C
C=O C=C
C-H

aliphatic
C-H

aromatic
C-H

Straw

300-1
300-2
300-3

300-5

Absorbance [arbitrary units]

availability of P in biochar decreased with increasing

temperature despite an increase in total P [35]. In comparison
with char from other organic materials such as greenwaste,
wood [36e38], biochar from rice straw is higher in pH, nutrient
contents and CEC. And compared with the original rice straw,
there are 29.1% P, 79.3% K, 31.8% Ca, 57.2% Na and 24.4% Mg of
total content still preserved as available forms in RSD biochar
produced at 400
C. These results suggest that RSD biochar
might be more suitable as a potential fertilizer and amendment for soils through direct nutrient additions or nutrient
retention. The high pH and alkalinity of RSD biochar can
potentially neutralize soil acidity and increase soil pH to
ameliorate soil acidity. This would further decrease
exchangeable Al in soil to alleviate the possible toxic effects
[39]. CEC is indicative of the capacity of soil to retain key
nutrient cations in plant-available form. Oxidized functional
groups on biochar particles could lead to high CEC and charge
density to retain cations [18]. Lehmann et al. [40] found that
nutrient retention was caused by adsorption to an exchange
complex created by the charcoal additions. The normal CEC
ranges in soils would be from <3 cmolc/kg for sandy soils low
in organic matter to >25 cmolc/kg for soils high in certain
types of clay or organic matter [41]. Hence, low-temperature
RSD biochar which contained more oxygen-containing functional groups (Fig. 2) and a higher CEC, can enhance the
adsorption ability to retain cationic nutrients. Overall, rice
straw biochar produced at 400
C show the greatest potential
for use as soil amendment to improve the fertility of highly
weathered and infertile soil. However, as those methods were
soil specific analysis and no specific analysis methods developed for testing biochar up to now, these results might be
unable to truly reflect the function of biochar in complex soil
environment. Experiments taking soileplant interaction into
account should be carried out to verify the function of biochar
in actual application.
Compared with charring temperature, residence time had
less influence on the characteristics of RSD biochar produced
in this study. However, other research on bamboo, rice straw,
honey mesquite derived charcoal showed that residence time
is the second most important factor affecting the chemical,
physical, morphological and spectral properties of biochar,
and the effects of residence time on biochar characteristics
were similar to the effect of temperature [21,42,43]. The
different process condition (heating rate) might contribute to
the different results.

400-1
400-2
400-3
400-5

500-1
500-2
500-3
500-5

600-1
600-2

600-3

600-5

700-1
700-2
700-3
700-5

4000 3600 3200 2800 2400 2000 1600 1200 800

-1
Wavenumber [cm ]

400

Fig. 2 e Stacked FTIR spectra of RSD biochars generated at

temperatures ranging from 300 to 700
C and different
residence time.

C and O/C ratios compared with rice straw clearly showed that
rice straw underwent progressive dehydration and depolymerization. Hemicellulose and cellulose are the main
components of rice straw. As their decomposition is much
easier than that of lignin during the pyrolysis process [49], it
could be the main reason why weight loss and H/C, O/C of rice
straw biochar was more significant in this study than those of
wood or grass under the same temperature and residence
time [30]. Despite these chemical changes, it is evident that
the pyranose structures of cellulose are still preserved

273

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

3.3.

XRD of RSD biochar

The X-ray diffraction patterns of the RSD biochars are displayed in Fig. 3. All biochars had analogous diffractogram
patterns. However, some slight differences were noted
amongst the samples. Compared with Power Diffraction and
Standards (PDF), these sharp peaks in the RSD biochars indicate the presence of inorganic components such as SiO2, KCl
and CaCO3. As reported by other researchers, different feedstock such as wood, grass, corn straw, peanut straw [30,52,53]
resulted in various crystal components. Compared with other
materials, rice straw is low in lignin and high in Si and K
[32,54,55], which gives rise to a high content of SiO2 (peaks at
4.27, 3.35 
A) and KCl (peaks at 3.14, 2.22 
A) in RSD biochars.
With the increase of charring temperature from 300 to 500
C,
the peak at 3.04 
A was intensified, indicating that the calcite

4.27

3.35
3.14
3.04

2.21
1.82
300-1
300-2
300-3
300-5

400-1

400-2
400-3

Diffraction Intensity

(CeOeC skeletal vibrations in pyranose ring at 1080 cm1). 15

(2q) assigned to hkl 101 crystallographic planes of completely
ordered (i.e. crystalline) regions of cellulose is retained in the
XRD spectra. This illustrates that the cellulose still had
a portion of its crystallinity.
With increasing charring temperature, bands due to OeH
stretching (3200e3600 cm1) and aliphatic CeH stretching
(2950e2850 cm1) lose their intensity, but bands arising from
aromatic CeH out of plane vibrations (700e900 cm1) became
more apparent. This implies that greater dehydration and
increased aromatization occurred in this temperature range
[44]. Concurrently, cellulose-derived transformation products
are reflected in more prominent peaks at 1440 (aromatic C]C
skeletal vibrations) and 1375 cm1 (CeH deformation modes
in alkenes) [44] as a result of the decomposition and condensation of the cellulosic and lignin components.
At the high temperature, the graphene-like sheets formed at
the expense of aromatic C. Keiluweit and Uchimiya [30,50]
found that all C functionalities diminished at 700
C and the
FTIR spectrum resembled that of pure graphite. Antal [29] noted
that FTIR spectra of many carbonized charcoals resembled that
of graphite at 950
C. In this research, intensity of bands
declined when the charring temperature increased to over
600
C, except for CeO stretching (1080 cm1) which still sustained a strong presence even at 700
C. This was also observed
in cornstover char which was produced at 700
C from gasification [51]. This can be explained by the presence of pyranose
rings and guaiacyl monomers of cellulose and hemicellulose.
The FTIR data demonstrated that the formation of intermediates and increased aromatization occurred as rice straw
was heated to 400 and 500
C. With progressively increasing
temperature, the rice straw biochars tended to graphene-like
structure, but still sustain a pronounced O-contained functionality. Residence time had little influence on FTIR spectral
properties of RSD biochars. With the tendencies to graphenelike structures at higher temperatures, most of the remaining
non-C atoms were removed. Biochar shows the reverse trend
of oxidation and becomes less hydrophilic. The stability of
biochar may be increased for two reasons: first, the refractory
forms of graphene-C might indicate the more graphene-like
structures the higher stability; second, the possibility of
accelerated decomposition caused by non-aromatic fraction
of biochar through co-metabolism may be declined [31].

400-5

500-1

500-2
500-3

500-5
600-1
600-2

600-3

600-5

700-1
700-2
700-3
700-5

10

20

30

40
50
Two-Theta(2 )

60

70

80

Fig. 3 e X-ray diffraction (XRD) profiles of RSD biochars

generated at temperatures ranging from 300 to 700
C and
different residence time (d values given in A).

(CaCO3) content of biochar increased. However, it then

decreased and disappeared at high temperature of 600e700
C.
The peak at 15
(2q), which was assigned to hkl 101 crystallographic planes of completely ordered (i.e. crystalline)
regions of cellulose, remained distinct at 300
C, but was
absent at other charring temperatures. Peaks situated at
approximately 23
(2q) correspond to the diffuse graphite (002)
bands [52,56]. As the charring temperature increased from 300
to 400
C, the (002) band shifted from 21.5 to 23
(2q). Further
heating had no significant influence on the (002) peak position
but made it sharper and more symmetrical. In contrast, the
broad peak at 44
(2q) correspond to the (10) band [56], which is

274

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

attributed to graphite-like atomic order within a single plane,

appeared in all RSD biochars when the charring temperature
was raised to 600
C. Residence time also had little impact on
the atomic structure of the rice straw biochar.
The loss of peaks at 15
and the shift of (002) band at charring
temperatures of 300e400
C indicated the decomposition of
cellulose. This was consistent with the results from FTIR
spectra that showed the transformation products formed in
this temperature range. Although changes in functional groups
were observed with continual increase of charring temperature, no significant changes in the XRD patterns were detected,
except for some small differences with respect to peak shape
and intensity. Further heating resulted in the narrowing and
symmetry of (002) and the formation of (10) bands. This indicated that the development of atomic order and crystallite size
in the increasingly carbonized rice straw was accelerated by the
increasing charring temperature. But these small graphene
packets are still arranged in turbostratic disorder and, therefore
referred to as turbostratic crystallites. These results are
consistent with the turbostratic crystallites found in carbonized tall fescue straw [30].
To summarize, the XRD band patterns of RSD biochars are
indicative of an amorphous material having a poorly crystalline, carbon-rich phase. The turning point at which rice straw
loses cellulose crystallinity and evolves turbostratic crystallites

is 400
C, while 600
C is important for carbonized rice straw to

increase the degree of graphitization. The high stability of
amorphous and turbostratic crystallites due to the unordered
structure [48] may contribute to the recalcitrance of biochar
produced at relatively low temperatures. While the graphenelike atomic structure could be one reason for stability of biochar at high temperature (600
C). But the factual relevances
of the crystal structure of biochar for its recalcitrance are not
well documented and warrant further research.

3.4.

Solid-state

13

C NMR spectroscopy

The solid-state 13C NMR spectra (Fig. 4) of the RSD biochar

produced at 400 and 500
C for 3 h were dominated by one
peak at 130 ppm which is characteristic of aromatic C. Based
on the percentage of total C, the aromaticity content
(165e90ppm) of RSD biochar produced at 400
C accounted for
82.9%, 12.8% of which represented the aromatic CeO
(165e145ppm). And the alkyl and carboxylic C content were
7.5% and 9.6%, respectively. In contrast, heating to 500
C
resulted in a higher aromatic C content (98.5%, and 24.7% of
which represented the aromatic CeO) and lower amount of
alkyl C (1.5%), and no signal in carboxylic C region. This result
follows the general trends seen in previous charring studies
that the degree of aromaticity of biochar increased with

Fig. 4 e Solid state 13C CP and DP NMR spectra of RSD biochar produced at 400 and 500
C for 3 h. The position of spinning
sidebands is marked with an asterisk (*).

b i o m a s s a n d b i o e n e r g y 4 7 ( 2 0 1 2 ) 2 6 8 e2 7 6

increasing of pyrolysis temperature [34,44,57,58]. The Osubstituted aryl C most likely ascribe to the lignin structures
remained. Disappearance of carboxyl C can partially interpret
the rapid decrease of CEC from 400 to 500
C.
This result has significance for the stability of rice straw
biochar in soil. Cheng et al. [23]found that black locust biochars were dominated by aryl and O-aryl C, and abiotic and
biotic processes did not significantly increase O-aryl or
carboxylic C groups after incubating for 4 months. Biochar
collected from a wide range of climatic conditions and soils
also showed that the stability of biochar was primarily due to
its inherently recalcitrant chemical composition (highly
condensed aromatic C) [59]. Combined with the results of FTIR
and XRD, we assume that 500
C was high enough to convert
biomass to recalcitrant biochar. However, biochar produced at
lower temperature and from herbaceous plant was prone to
decomposition, even though there was only a small difference
between the aryl C content [60]. Given the similar NMR spectra
of biochar produced from different feedstocks, the cause of
this observation warrants further investigation.

4.

Conclusion

It is critical to control pyrolysis temperature rather than

residence time for producing desirable properties of biochars
using rice straw as a raw material at low heating rate. Nutrient
contents, CEC, available P and the extractable cations of rice
straw-derived (RSD) biochars decline, while alkalinity and
aromatic structure increase, with the increasing charring
temperature. For improving soil quality, RSD biochar generated at 400
C might be a better option. However, the higher
charring temperature may also result in a recalcitrant RSD
biochar. Before the widespread adoption of RSD biochar as
a soil amendment could be recommended, further studies are
needed to test RSD biochar stability and effect of biochar on
soil quality. Simultaneously, the life-cycle/socioeconomic
analyses should be considered.

Acknowledgements
This research was supported by the National Natural Science
Foundation of China (40873059, 41271247), the Specialized
Research Fund for the Doctoral Program of Higher Education
(20110101110083), the Natural Science Foundation of Zhejiang
Province (R5100044), the Environment Protection Agency of
Zhejiang Province, China (No. 2011B12) and the China Postdoctoral Science Foundation (20110491777). The NMR analysis
was performed in the Solid-State Nuclear Magnetic Resonance
Laboratory, Nanjing University. We sincerely thank Xiaokang
Ke at Nanjing University for assistance on NMR analysis.

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