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Pyrolysis temperature influences the characteristics of rice straw and husk bi‐
ochar and sorption/desorption behaviour of their biourea composite

Shiv Vendra Singh, Sumit Chaturvedi, V.C. Dhyani, Govindaraju Kasivelu

PII: S0960-8524(20)30946-9
DOI: https://doi.org/10.1016/j.biortech.2020.123674
Reference: BITE 123674

To appear in: Bioresource Technology

Received Date: 25 April 2020

Revised Date: 8 June 2020
Accepted Date: 10 June 2020

Please cite this article as: Vendra Singh, S., Chaturvedi, S., Dhyani, V.C., Kasivelu, G., Pyrolysis temperature
influences the characteristics of rice straw and husk biochar and sorption/desorption behaviour of their biourea
composite, Bioresource Technology (2020), doi: https://doi.org/10.1016/j.biortech.2020.123674

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1 Pyrolysis temperature influences the characteristics of rice straw and husk
2 biochar and sorption/desorption behaviour of their biourea composite
3 Shiv Vendra Singh1, Sumit Chaturvedi1*, V.C. Dhyani1, Govindaraju Kasivelu2

4 1Department of Agronomy, G.B. Pant University of Agriculture and technology, Uttarakhand, India
5 2Centre for Ocean Research, Sathyabama Institute of Science and Technology, Chennai- 600 119, India
6 Corresponding author: sumitagronomy78@gmail.com (Dr. Sumit Chaturvedi)
7 Abstract
8 Biochar obtained by biomass pyrolysis has several energies, environmental, and agricultural
9 applications. In the present study, influence of pyrolysis temperatures (300 °C, 450 °C and 600
10 °C) on characteristics of rice residue biochar and sorption/desorption pattern of biourea was
11 investigated. Biochar yield was reduced with the increasing temperature accompanied with
12 increasing carbon content, pH, and electrical conductivity. Elemental O:C and H:C ratios of
13 biochar decreases with temperature. Half-life was predicted between 500-750 years varying
14 positively with pyrolysis temperature. Urea sorption/ desorption studies revealed ˃90 % sorption
15 in both rice straw and husk biochar with highest urea adsorption at 450 °C, while desorption was
16 more sustained in rice straw biourea. Microporosity, cation exchange capacity and functional
17 groups primarily carboxyl and keto group, played key role in sorption/desorption pattern of
18 biourea with slow release kinetics. Rice residue based biourea composites have potential to raise
19 the crop yields and nitrogen use efficiency.
20 1. Introduction
21 The thermochemical conversion of biomass in limited or absence of oxygen condition is
22 showing a promising way of agro-waste valorisations. The Pyrolysis have industrial perspectives
23 for judicious utilization of agro-waste by optimizing the conditions as per the desirable products
24 viz., liquid, solid (char or biochar), or gas production. It has been practiced since ages to produce
25 biochar from biomass (Amutio et al., 2012). Thermo-chemical decomposition in pyrolysis
26 converts biomass into a network of carbonates and aromatic compounds. It is an aromatic ‘C’
27 rich biomass produced under limited oxygen supply or its absence (Lehmann and Joseph, 2009).
28 Biochar production and utilization have gained worldwide attention as a carbon-negative
29 technology of residue/waste management for sustained and diversified utility in agriculture
30 system (Saadat et al., 2018). Inexpensive accessibility, huge surface area and pore volume of
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31 biochar favours its application for sustained nutrient supply (Dong et al., 2019; Liu et al., 2019),
32 environmental remediation (Chen et al., 2018), heavy metal removal (Ahmad et al., 2014;
33 Gwenzi et al., 2017), soil remediation (Zhou et al., 2017; Yin et al., 2018) etc. Surface area and
34 porosity of biochar increases with increase in pyrolysis temperature (Yu et al., 2019). Several
35 organic wastes are being used for production of biochar through pyrolysis at a temperature
36 between 300 °C to 800 °C (Mukherjee and Zimmerman, 2013).
37 Lignocellulosic waste of woods, crops and their co-products, problematic weeds, aquatic
38 plants/weeds, municipal and animal wastes, are nowadays considered as a potential source of
39 renewable energy production through the process of pyrolysis. India is the second-largest
40 agrarian economy and generates a large amount of agricultural waste, including 500 MT/year of
41 crop residues (GoI, 2016). The majority of crop remnant produced in India are rice and wheat
42 straw, maize stover, sugarcane trash, millets, pulses, oilseeds, fibre crops and some residue of
43 agricultural industries like rice husk, cotton waste, groundnut shell, coir pith, bagasse, etc.
44 (Sugumaran and Sheshadri, 2009). The dearth of suitable technologies and a huge volume of
45 biowaste are the significant reasons for widespread burning, which in turns leads to energy
46 wastage, greenhouse gases (GHGs) emission, air and water pollution, soil health decline and
47 nutrient loss and human health problems (Bhuvaneshwari et al., 2019). On-farm burning is also
48 especially aggravated in rice -wheat belt of Indo-gangetic region (IGP) due to the short
49 turnaround period, the practice of clean cultivation, ease of farm mechanization, and pest
50 management (Bhuvaneshwari et al., 2019). Thermal decomposition of biomass into pyrogenic
51 carbon (PyC), therefore, can be one of the promising techniques to address the ill effects of
52 burning. PyC can enhance the soil water holding capacity, CEC, nutrient retention and lower the
53 bulk density of soil which collectively increases the crop productivity (Lehmann et al., 2011; El-
54 Naggar et al., 2018). The magnitude of improvement in soil health is greatly influenced by the
55 amount of biochar and its properties (Lehmann et al., 2011; Bista et al., 2019).
56 Besides feedstock, pyrolysis conditions viz., temperature, solid and vapour residence
57 time, heating rate, and carrier gas flow rate also influences biochar yield and its properties.
58 During pyrolysis, aliphatic carbon chains of feedstocks are converted into aromatic carbon and
59 other co-compounds called polyaromatic hydrocarbons (PAHs) (Spokas et al., 2011) are
60 produced. As the temperature increase with the time, aromatic ‘C’ planes are formed connected

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61 to aliphatic chains (Keiluweit et al., 2012) known as fixed carbon (FC). Volatile organic
62 compounds (VOCs) developed during pyrolysis as intermediate products with FC are considered
63 as labile fraction (Yargicoglu et al., 2015). The proportionate ratio of FC and VOC are broadly
64 pyrolysis conditions and feedstock dependent (Wiedner et al., 2013). Biochars of low pyrolysis
65 temperature have higher readily decomposable volatile matter content (Robertson et al., 2012)
66 whereas, the biochars of high temperatures have higher surface area and aromatic carbon, which
67 increases its adsorption capacity as well as the recalcitrance nature (Spokas, 2010).
68 The primary plant nutrient, nitrogen is essential for plant growth mainly nourished with
69 synthetic fertilizers. These synthetic nitrogen fertilizers are prone to high N losses as leaching,
70 volatilization and nitrous oxide emissions (Zhang et al., 2015). These losses collectively cause
71 low nitrogen use efficiency (NUE), higher production costs and environmental pollution, more
72 specifically greenhouse gas (GHG) emission. Quite a few slow-release nitrogenous fertilizers
73 (SRNF) have been developed using diverse coating materials as a membrane serving diffusion
74 barrier. Slow-release fertilizers (SRF) offer a gradual nutrient release to accord the supply with
75 the crop nutrient demand for growth and development. SRFs use is associated with several
76 economic, agronomical, and environmental returns and saving of spreading costs. Various
77 polymers viz., wax, sulfur, cellulose, lignin, sodium alginate etc. are being used as encapsulating
78 materials however; none has expanded at commercial scale due to one or other limitations (Ni et
79 al., 2011).
80 Biochar with high porosity and multiple-functional groups are widely investigated for
81 utilization as sorbent material for pollutants removal such as pesticides, heavy metals, and
82 hydrocarbons. The same could be utilized to increase nutrient retention/sorption (O'Connor et al.,
83 2018) however, only few reports have focused on nutrient retention and release dynamics. Thus,
84 the present study was performed to evaluate the structural modification, physico-chemical
85 properties, half-life and urea sorption/desorption potential of biochar derived from rice straw and
86 husk biomass wastes at variable pyrolysis temperature.
87 2. Materials and methods
88 2.1 Collection and preparation of feedstock’s
89 Organic waste of rice straw (RS) and rice husk (RH) was collected from the Norman E.
90 Borlaug Crop Research Centre, G.B. Pant University of Agriculture and Technology, Pantnagar,

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91 Uttarakhand (28.97°N 79.41°E). The collected raw material of rice straw was chopped into small
92 pieces (0.5 - 1 cm) and oven-dried (70 °C) for 48 h and after that ground and pass through 20
93 mesh sieves (particle size < 1 mm).
94 2.2 Biochar production (pyrolysis) and % biochar yield
95 Pyrolysis of prepared feedstock was carried out in batch type reactor under oxygen-
96 limited conditions (Mandal et al., 2018). 200 g of sun-dried feedstock was loaded in the
97 container of the reactor. CO2 was purged inside the reactor prior to feedstock loading with a flow
98 rate of 3 L min-1. The flow rate of CO2 purge was measured by using meter devise with a
99 specific range of 0.1–3 L min-1. As the gas flow stabilizes, the temperature was set to the desired
100 pyrolysis temperature (300 °C, 450 °C, and 600 °C) for biochar preparation. Biochar samples
101 derived from rice straw produced at 300 °C, 450 °C, and 600 °C were thereafter called RSB-300,
102 RSB-450, RSB-600, and similarly, rice husk derived biochar at 300°C, 450 °C, and 600 °C as
103 RHB-300, RHB-450, and RSB-600, respectively. The biochar yield (%) or carbon recovery (%)
104 for each feedstock, and each pyrolyzing temperature was calculated.
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑏𝑖𝑜𝑐ℎ𝑎𝑟 𝑜𝑏𝑡𝑎𝑖𝑛𝑒𝑑
105 % 𝐵𝑖𝑜𝑐ℎ𝑎𝑟 𝑌𝑖𝑒𝑙𝑑 = 𝑀𝑎𝑠𝑠 𝑜𝑓 𝑓𝑒𝑒𝑑𝑠𝑡𝑜𝑐𝑘 𝑙𝑜𝑎𝑑𝑒𝑑 × 100 (1)

106 2.3 EC, pH and CEC of biochar

107 The pH and electrical conductivity (EC) of all the feedstock’s used for pyrolysis and their
108 respective biochar derived at different temperatures were measured using ESICO-1615, a
109 microprocessor-based pH-EC-TDS meter. The pH of feedstock’s and their respective biochar
110 was measured by placing 1 g of sample in a 100 ml beaker followed by the addition of 20 mL of
111 deionized water. The shaking of the solution was done for 10 min by using a rotary shaker and
112 allowed to stand for 5 min before measuring the pH (Bordoloi et al., 2015). The electrical
113 conductivity of the same solution was measured after allowing them to stand overnight. The
114 cation exchange capacity (CEC, cmol/kg) is a measure of the quantity of surface negatively
115 charged sites that can hold cations such as calcium (Ca2+), magnesium (Mg2+), and potassium
116 (K+), by means electrostatic forces. Electrostatically retained cations are easily exchangeable in
117 the soil solution, therefore higher values indicating greater ability to maintain Ca2+, Mg2+, and K+
118 than a soil with a low CEC. CEC was calculated by determining the displaced cations or
119 quantifying the amount of addition in cation using the Barium (Ba2+) and ammonium (NH4+) as
120 exchanger cations.

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121 2.4 Proximate Analysis and ultimate analysis
122 Moisture content, volatile matter, fixed carbon, and an ash content of feedstocks and their
123 respective biochars was determined through proximate analysis according to the protocols for
124 chemical analysis of coal and cake (ASTM D3172-13, 2013), on a dry weight basis. After
125 determining the moisture content (MC), volatile matter (VM), and ash content, the rest of the
126 weight difference was considered as fixed carbon (FC) content.
(𝐴 ― 𝐵)
127 (𝑖)𝑀𝑜𝑖𝑠𝑡𝑢𝑟𝑒 (%) = 𝐴 × 100 (2)

(𝐵 ― 𝐶)
128 (𝑖𝑖) 𝑉𝑜𝑙𝑎𝑡𝑖𝑙𝑒 𝑚𝑎𝑡𝑡𝑒𝑟 (%) = 𝐵 × 100 (3)
129
(𝐶 ― 𝐷)
130 (𝑖𝑖𝑖) 𝐴𝑠ℎ 𝐶𝑜𝑛𝑡𝑒𝑛𝑡 (%) = 𝐶 × 100 (4)
131
132
133 Where, A= grams of air-dried sample
134 B= grams of the sample after drying at 105°C for 2 hours
135 C= grams of the sample after drying at 950°C for 6 minutes
136 D= grams of residue after drying at 750°C for 6 hours
137
138 (iv) Fixed Carbon (%) = 100 - (Moisture + Volatile matter + Ash)

139 2.5 Elemental analysis

140 Elemental analysis of both the biomass and biochar derived at different temperature were
141 carried out. Carbon (C), Hydrogen (H), Nitrogen (N), and Sulphur (S) were analyzed in a CHNS
142 analyzer. Oxygen (O) was determined by the difference of mass, considering that the whole
143 biomass is composed of C, H, N, S, O, and ash (D3176-09, 2013).
144
145 2.6 SEM, EDS and FT-IR analysis
146 Scanning Electron Microscopy (SEM, Hitachi S-4800) and Energy Dispersive X-ray
147 Spectroscopy (EDS) (Oxford Instruments) were performed for structural, morphological
148 characterization, the elemental composition of biochar and biourea. Information about the
149 presence of a variety of functional groups on biochar and biourea was obtained through Fourier
150 transforms infrared (FT-IR) analysis at 4000–600 cm-1 spectral arrays.
151 2.7 Urea sorption and desorption study
5
152 Stock solution of Urea (2000 ppm) was prepared in distilled water and it was further
153 diluted to desired concentrations ranging from 10 to 2000 ppm. Biochar of rice straw and husk
154 used for urea sorption were produced at 300 °C, 450 °C and 600 °C temperature and passed
155 through 60 mesh sieves after grinding and added to prepared urea solution. Final urea-biochar
156 solutions were wrapped and subjected to water bath shaking at 30 °C on spinning speed of 80
157 rpm to reach at sorption equilibrium, to establish the correlation between equilibrium curves of
158 the solid and liquid phase and to find out the isothermal constants of Freundlich adsorption
159 isotherm. Linear form of the multilayer adsorption isotherm for heterogeneous surfaces;
160 Freundlich isotherm was expressed as:
161 Qe = KFCe1/n (5)
162 Where,
163 “Qe” is the urea concentration at solid-phase equilibrium (mg/kg),
164 “Ce” is the urea concentration at liquid phase equilibrium (mg/L),
165 “KF” is sorption balance constant, and
166 “n” is exponential parameter
167 Adsorption isothermal parameters for all the biochar samples used were calculated by
168 linear regression analysis. “KF” and “n” were taken as evaluation criteria for sorptivity.
169 The desorption pattern of urea adsorbed biochar was performed by taking the filtrate of
170 different reaction products (biourea). After the addition of bio-urea samples in distilled water and
171 urea content in the extracted solution for different time intervals were observed at a wavelength
172 of 527 nm (Kumar and Aggarwal, 1989). The desorption experiment was executed for 72 h, and
173 the extract was collected at frequent intervals from 0 min to 72 h. Collected samples were
174 analyzed for urea concentration in collected leachates for cumulative release under the same
175 equilibrium conditions. The bio-urea sample for each biochar with maximum urea content was
176 taken for release study. Batch experiments were done using 1000 mg of bio-urea in a conical
177 flask suspended with 20 mL distilled water and marked for each sampling. Similarly,
178 observations were taken till 72 h, and urea content in the filtrate was determined similarly as for
179 urea sorption. Urea content in the collected samples was recalculated with the standard curve of
180 urea (y = 0.01x + 0.0225, R2 = 0.99) using the sample absorbance values.
181
182 2.8 Statistical analysis
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183 The data are presented as mean ± standard error difference (n = 3). Analysis of variance
184 was undertaken to determine significant differences between the treatments, with significant
185 difference considered at p < 0.05.
186
187 3. Results and Discussion
188 3.1 Characterization of feedstock
189 Proximate and ultimate analysis of feedstocks is presented in Table 1. EC (dSm-1) of rice
190 straw and husk was recorded to be 0.68 and 0.59 and pH 8.10 and 6.5, respectively. Moisture
191 content in the sun-dried biomass of both the feedstock was 5 - 6 %; however, VM was higher in
192 rice husk (64.93 %) than rice straw (60.47 %). Fixed carbon in the biochars viz., rice straw and
193 husk ranged from 11.07 - 12.93 % and 18.37 -20.06 %, respectively. The high VM and low ash
194 contents indicate a remarkable conversion to pyrogenic vapor during thermal treatment and low
195 biochar yield (Yu et al., 2019). Biomass with higher volatile matters is desirable for bio-oil
196 production along with biochar (rice husk). Ultimate analysis representing the carbon, hydrogen,
197 sulfur, oxygen, and nitrogen and elemental ratios of both the feedstock’s relating the qualitative
198 traits (Table 1). C, H, N, S, and O content of rice husk was recorded 43.3, 3.22, 0.8, 0.05, and
199 40.9 %, while for rice straw values were 41.3, 6.1, 1.0, 0.5, and 37.0 %, respectively. Elemental
200 ratios viz., H:C, and O:C ratios of rice husk and straw were 0.89 & 1.78 and 0.71 & 0.68,
201 respectively. As the structural compositions of feedstock are straightly related to the properties of
202 biochar and its stability. Feedstocks with higher H:C ratio and lower O:C ratio gives the stable
203 biochar production.
204
205
206 3.2 Chemical properties of biochar
207 The physicochemical properties of biochars prepared at different temperature are shown
208 in Fig 1. The pH and electrical conductivity of biochars derived from rice straw and husk
209 increased with an increasing pyrolysis temperature. Emanation volatile matter (acid functional
210 groups) and development of alkali functional groups can be the probable reason of elevating pH
211 and EC (Zhao et al., 2017). Temperature favours the formation of the Si–C bonds, thereby
212 increasing the number of aromatic components and recalcitrance of the biochar. Increase in the

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213 relative concentration of non-pyrolyzed inorganic elements and ash content elevates the pH
214 (Jung et al., 2016). Cation exchange capacity (cmol/kg), a substantial property for ionic sorption
215 capacity of biochar decreased from 24.4 to 17.3 and 39.6 to 24.7 in both the feedstocks (rice
216 straw and rice husk, respectively) with the increase in temperature from 300 °C to 600 °C. A
217 decrease in cation exchange capacity with elevating pyrolysis temperature was also reported in
218 rice husk (Phuong et al., 2015); rice straw biochar and apple wood biochar (Zhao et al., 2017).
219 Proximate analysis as an approach of recalcitrance evaluation of biochars is largely
220 temperature dependent (Table 1). Carbon recovery (% biochar yield) decreased with the
221 increasing temperature in both the feedstocks. Higher recovery was recorded with rice husk than
222 rice straw at each temperature. In the study, increase in pyrolyzing temperature reduced biochar
223 yield from 38.23 to 27.14% and 43.32 to 37.30% and the volatile-matter content from 38.23 to
224 27.14% and 43.32 to 37.30% for RSB and RHB, respectively. Two distinct pools of carbon in
225 biochar (labile and non-labile pool) are represented by volatile matter and ash content,
226 respectively (Lehmann and Joseph, 2009). The biochar yield and volatile content was reduced as
227 these are negatively correlated with temperature (Li et al., 2018). A decrease in biochar yield
228 with the increasing temperature may be attributed to increase in de-volatilization of organic
229 compounds, dehydration of hydroxyl groups and decomposition of lignocellulose (Gomez et al.,
230 2016). Rice straw contains a higher amount of Si (Soest, 2006), which is associated with the ash
231 content of the biochar. The ash content and fixed carbon (Table-1) increased with the rising
232 temperature due to thermal decomposition of labile fraction, enhancing the proportion of
233 minerals. Fixed carbon is regarded as the recalcitrant carbon or non-labile carbon fraction
234 remains after thermal degradation (Lehmann and Joseph, 2009) is chiefly influenced by the
235 feedstock. Both the feedstocks showed an increase in fixed carbon content with the increment in
236 temperature (Zhao et al., 2013). Feedstocks with higher volatile and ash content produce the
237 biochar with higher fixed carbon. The volatile content of PyC equates with a labile component
238 and less VM with higher FC are considered to have higher stability or resistance for
239 decomposition.
240 Ultimate analysis representing the organic fraction and elemental ratios for C, H, N, S
241 and O relates the qualitative traits of resultant biochar (Table-1). With the increasing temperature
242 hydrogen, nitrogen, sulfur and oxygen content was reduced while C content increased in both the

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243 feedstocks. The contents of C, H, N, S and O for rice straw biochar ranged from 64.74 - 68.15
244 %, 2.8 - 1.31 %, 0.74 - 0.59 %, 0.16 - 0.06 % and 12.84 - 6.43 %, while same in case of rice husk
245 biochar were 65.51 - 69.02 %, 2.63 - 0.93 %, 0.92 - 0.52 %, 0.08 - 0.01 % and 11.09 - 5.29 %,
246 respectively. As the temperature increases, elemental ratios H:C, O:C and (N + O):C gradually
247 declined, reflecting the loss of hydrogen and oxygen content. It suggests increased
248 hydrophobicity and aromaticity as also indicated by Rafiq et al., 2016. Lower C:O ratio indicates
249 forming a stable crystal graphite-like structure with the arrangement of the aromatic rings
250 structure. Higher temperature caused the decomposition of the functional groups through
251 degradation (supplementary fig. S1). Reduction in H:C and O:C ratios (Table 1) are the results of
252 dehydration and decarboxylation reactions. Biomasses naturally contain labile and recalcitrant
253 fractions; the former hastily vanishes during initial heating while the latter is left in the final
254 product. The structural composition of feedstock is directly related to the properties of biochar
255 and its stability because H:C and O:C ratios depicting aromatic and volatile content is subjected
256 to thermal degradation during pyrolysis (Cui et al., 2016). Volatile matter and fixed carbon are
257 considered as an approximation of carbonaceous substances. These ratios are used to determine
258 the degree of aromaticity and maturation and these ratios provide a dependable measure of both
259 the degree of pyrolysis and oxidative adjustment of biochar.
260 3.3. Elemental ratios and stability
261 A Van Krevelen diagram (Figure-2), plotted with H:C molecular ratio against O:C
262 molecular ratios of biochars derived from rice straw and husk at different pyrolysis temperature
263 and biomass represent that biomass undergoes dehydration, increasing aromaticity and
264 depolymerization. The molar H:C and O:C ratio are correlated with the degree of
265 thermochemical alteration that produces fused aromatic ring structures and these structures are
266 the measures of biochar’s stability (Schimmelpfennig and Glaser, 2012). Uppermost H:Corg and
267 O:Corg limit of 0.7 and 0.4, respectively are standardized by European Biochar Certificate
268 (EBC) guidelines to discriminate biochar from partially or non-thermochemically altered
269 biomass (Schimmelpfennig and Glaser, 2012). Similarly, H:C and O:C ratios for biochar ranged
270 between 0.52 - 0.16 and 0.39 - 0.29, respectively in the present study while the same for biomass
271 used for biochar production was 1.89 - 0.85 and 0.89 - 0.69, respectively. Figure - 2 showed the
272 decreasing H:C and O:C ratios of biochars with increasing pyrolysis temperature. The higher

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273 range of O:C molecular ratio was recorded in biochar derived at lower pyrolysis temperature
274 (300 °C) and low stability. Similar findings were also reported by Singh et al., 2012. It is
275 hypothesized that biochar with high H:C and lower O:C ratios are more stable and higher O:C
276 ratio recommends more oxygen-based functional groups and hydrophilic surface (Cui et al.,
277 2016). Prediction for half-life of biochar made by Spokas (Spokas, 2010) suggest that, O:C > 0.6
278 will probably possess a half-life <100 years, half-life of between 100 – 1000 years correspond to
279 O:C 0.2 - < 0.6, while O:C ratio < 0.2, the resulting biochar that may persist a half-life of greater
280 than 1000 years. In the current study, O:C ratios for all the biochar was around 0.3 - 0.4 which
281 suggest that the stability of rice straw and husk biochars can be predicted for the half-life of 500
282 to 750 years. Biochar obtained at 300 °C have O:C molar ratio between 0.40 - 0.35 were
283 predicted to have half-life of 500-625 years while biochar derived at 450 °C and 600 °C cover
284 O:C molar ratio 0.35-0.30 and are projected with half-life of around 625-750 years or more.
285 Pyrolysis temperature being considered as a criterion for biochar stability however, the O:C
286 molecular ratio also varies with heating rate and uniformity, residence time, cooling method used
287 and storage period. The adaptive approach of carbonizing surplus residues in agriculture
288 production system can reduce biomass burning and increase soil carbon sequestration.
289 3.4. Furrier Transform Infrared (FT-IR) Spectrum
290 The FT-IR spectrum of biochar and biourea composite of rice straw (RSBU) and rice
291 husk (RHBU) is presented in supplementary file Fig. S1 reflecting the changes in functional
292 groups composition of biochar and biourea. All the biochar showed a similar pattern on the FT-
293 IR spectra. Spectra represents primary amines N-H stretching (~3400, ~1462 cm-1), stretching at
294 3400 - 3500 cm−1 is attributed to -OH being overlapped by N-H group, aromatic (C-H), aliphatic
295 (C-O-C & O-H), aromatic (C=C & C=O), aromatic carbonyl/carboxyl (C=O), methylene and
296 methyl (C-H) stretching at ~815 cm-1, 1160–1030 cm-1, ~1600 cm-1, ~1700 cm-1, ~2860, ~1590
297 cm-1 and ~2930 cm-1, respectively (Sun et al., 2011). These peaks appeared present in each
298 biochar, but peaks for N-H groups disappeared in biochar except in biourea sample of both
299 RSBU and RHBU. Biochar showed a captivation band at 1383 cm-1 attributed to C=O stretching
300 vibration of carboxylic groups. FT-IR fields of RSBU and RHBU showed bands at ~1100, 1462
301 and 1682 cm-1 which are attributed to asymmetric stretching of C-NH-C, amine III C–NH, and

10
302 CH2–CO–NH–, respectively (Yang et al., 2014). Peaks of N-H (3450, 1462 cm-1) and C=O
303 (1611 cm-1), indicating the urea existence into the biochar (Liu et al., 2019).
304 3.5 SEM and EDS characteristics of biochar and biourea
305 The visual depiction surface morphology and composition of biochar is primarily
306 performed by SEM (Supplementary file Fig. S2 and Fig. S3) and biochar derived from rice straw
307 and husk showed a porous structure with smooth, tight, and tubular plane. The micro-porous and
308 tubular morphology of biochar favour it to store and retain nutrients and soil microorganisms and
309 reserve the water for dry periods. SEM images of RSBU and RHBU exhibited an abrasive and
310 undulating surface instead of the porous surface of biochar which indicates to filling of urea
311 particles in the micropores and cavities. Presence of many fissures, cracks and collapsed
312 locations in place of micropores and cavities are positively giving the conformity of urea
313 intercalation into the biochar (Liu et al., 2019). Energy-dispersive X-ray spectroscopy (EDS) of
314 biochar and biourea was carried out to determine their quantitative elemental composition. EDS
315 of the RSB and RHB showed atomic weight of N as 1.03 and 0.1 %, respectively while it was
316 5.80 and 4.40 %, respectively for RSBU and RHBU. It confirmed large potential for urea
317 sorption in biochar as reflected by increased N content in biourea.
318 3.6 Sorption Studies
319 Sorption balance constant (KF) and exponential parameter (n) of Freundlich adsorption
320 isotherm were taken as evaluation criteria for sorptivity. Adsorption isothermal parameters for all
321 the biochar used were calculated by linear regression analysis and are summarized in Table-2.
322 Solid and liquid phase urea concentrations of Freundlich isotherm are plotted in the graph
323 (figure-5) for liquid phase equilibrium (Ce mg L-1) vs solid-phase equilibrium (Qe mg kg-1) of
324 urea in their log values. A significant positive coefficient of determination ‘R2’ signifies the fit of
325 the experimental data to the equation.
326 The experimental data and graph specify that both the biochar exhibits high sorption
327 efficiency, with similar adsorption pattern at different temperature. Biochar derived at 450 °C
328 irrespective of feedstock’s displayed higher adsorption mainly attributed to the balance of
329 functionality, porosity and CEC. Adsorptivity reduced both at 300 and 600 °C with minimum
330 value observed at 300 °C. Exponential parameter “n” considered as the sorptivity evaluation
331 criterion and its higher value indicates easy sorption, while lower value means hard behaviour

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332 for sorption. RSB-450 and RHB-450 samples displayed easy sorption giving highest “n” value of
333 1.37. The “n” values were slightly lowered at 600 °C while it was lowest at 300 °C temperature
334 as shown in Table-2. The KF values depicting freundlich adsorption capacity varied from 2.24-
335 3.91, with highest value obtained at 450 °C for both rice straw and husk biochar. According to
336 Jhang et al., 2015, biochar produced at lower temperature of 300 °C showed better sorption for
337 urea at lower concentration (<4000 ppm) while the biochar of 500-600 °C have higher capacity
338 under high urea concentration (>4000 ppm). Cai et al., 2016 reported higher ammonium sorption
339 potential of biochar derived at 200-300 °C temperature. Some previous research also suggested
340 that the conversion of aliphatic structures to aromatic structures at 500 °C temperature, the
341 adsorptivity for organic macro-molecules increases (Kambo and Dutta, 2015).

342 3.7 Desorption pattern

343 Desorption pattern and cumulative nutrient released and from RSBU and RHBU were
344 studied through water incubation experiment and displayed in figure-3. One urea sorbed biochar
345 from both the feedstocks having highest urea sorption (RSB-450 and RHB-450) was taken for
346 desorption study. RHB-450 showed fastest Urea release within 72 h of the incubation period,
347 with almost 98% of urea released into the water. However, the rates of release from RSBU,
348 water declined, with the cumulative N release (91%) within the same period. A rapid release of
349 urea was recorded with RHB-450 and most of the urea released for 2900 minutes and thereafter
350 get plateau whereas in case RSB-450, increasing release trend was recorded upto 3600 minutes
351 (figure-4). Release process is the combination of dissolution of nutrient particle, adsorption and
352 their diffusion and SEM results, showing attachment of urea particles on the surface and their
353 adsorption within the cavities of biochar. These particles are bound to release into solution with
354 their dissolution and diffusion over the period. Liu et al (2019), also reported coinciding finding
355 for the release from the urea loaded biochar and bentonite composites. Swelling and spelling of
356 biochar with the absorption of moisture lead to the release nutrient particles intercalated nutrient
357 particles into the cavities of biochar. This phenomenon of swelling may be faster and higher in
358 case of RHBU than RSBU following the process of partial nutrient diffusion under the
359 concentration gradient. These biourea composites with controlled release pattern have potential
360 to address environment related concerns by increased fertilizer N efficiency and reduced
361 leaching losses.
12
362 4. Conclusions

363 RSB and RHB exhibited huge sorption potential for urea due to their continuous tubular,
364 micro-porous structure, high functionality, CEC and porosity. Elemental O:C and H:C ratios of
365 biochar decreases with increasing pyrolysis temperature. Its predicted half-life based on
366 molecular ratios was 500-750 years which varied positively with temperature. The adsorption
367 isotherm suggests that urea sorption was highest at 450 °C for both RSB and RHB, while
368 desorption was more sustained in RSBU than RHBU. The rice residue biochar with unique
369 sorption and desorption behavior and long half-life can be helpful to fabricate novel N fertilizers
370 and ensure soil carbon sequestration.

371 Acknowledgement
372 Authors thank ICAR-NICRA, CRIDA, Hyderabad, Government of India for funding the
373 Project under which the present research was undertaken.
374 Author Contributions
375 Conceived research: Sumit Chaturvedi. Designed and performed the experiments: Sumit
376 Chaturvedi, V C Dhyani and ShivVendra Singh. Analyzed the data: ShivVendra Singh and
377 Govindraju Kasivelu. Contributed to reagents/materials/analysis tools: Sumit Chaturvedi and
378 Govindraju Kasivelu. Wrote the manuscript: ShivVendra Singh. Finalized the manuscript: Sumit
379 Chaturvedi.
380 Conflict of interest
381 On behalf of all authors, the corresponding author states that there is no conflict of interest.

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517
518
519
520
521
522
523
524
525
526
527
528
529
530

18
531 Figure 1: Effect of temperature on (a) pH, (b) EC, (c) CEC and (d) C recovery (%) of
532 biochar produced from rice straw and rice husk at different temperature (300 °C, 450 °C
533 and 600 °C).
534
535 10.2 a b
RS 1.70 RS
10.0 RH RH
536 1.65
9.8

537 9.6 1.60

9.4
1.55

EC (ds/m)
9.2
pH

9.0 1.50

8.8
1.45
8.6

8.4 1.40

8.2
1.35
300 450 600
o
300 450 600
Temp ( C) o
Temp ( C)

44
RS
42 c RH
40
d
B
38 C
40 36

38 34
C recovery (%)

32
CEC (cmol/kg)

36
30

34 28

26
32
24
30 22

20
28
18
26 16
300 450 600 300 450 600
o o
Temp ( C) Temp ( C)

19
539 Figure-2: Van Krevelen diagram of biochar obtained at different temperature and
540 feedstock samples

541
542
543
544
545
546
547
548
549
550
551
552
553
554

20
555 Figure-3. Linear plots of intra-particle adsorption of urea by biochars produced at
556 different pyrolysis temperatures (A) RS-300, RS-450, and RS-600 (B) RH-300, RH-450 and
557 RH-600. Qe is the solid phase equilibrium concentration (mg/kg) and Ce is the liquid phase
558 equilibrium (mg/L).

559

21
561 Figure-4. Cumulative desorption pattern of urea from rice straw biourea (RSBU) and rice
562 husk biourea (RHBU) at 450 °C temperature.
563

564

565

566

567

568

569

570

571

572

573

574

575

22
576 Table-1: Proximate, Ultimate analysis and elemental ratios of feedstock and their respective biochars derived at different
577 pyrolysis temperature.

Feedstock Biochar
Parameters
Rice Husk Rice Straw RS 300 RS 450 RS 600 RH 300 RH 450 RH 600
Proximate analysis (%)
Moisture
5.6 ± 0.58 6.5 ± 0.52 3.2 ± 0.09 3.8 ± 0.07 4.2 ± 0.08 3.4 ± 0.09 3.9 ± 0.19 4.9 ± 0.17
Content
Volatile Matter 64.9 ± 2.50 60.5 ± 1.89 25.1 ± 0.97 18.5 ± 0.85 11.0 ± 0.54 24.4 ± 0.25 17.3 ± 0.27 10.2 ± 0.38
Ash 11.1 ± 1.03 13.0 ± 0.57 19.3 ± 0.16 22.0 ± 0.53 24.5 ± 0.61 20.5 ± 0.49 23.5 ± 0.71 25.5 ± 0.63
Fixed Carbon 18.4 ± 3.97 20.1 ± 2.19 52.3 ± 0.82 55.6 ± 1.37 60.3 ± 0.34 51.7 ± 0.66 55.4 ± 0.73 59.4 ± 0.29
Ultimate analysis (%)
Carbon 43.3 ± 2.09 41.3 ± 0.84 64.7 ± 1.03 67.2 ± 1.04 68.2 ± 1.63 65.5 ± 1.09 67.5 ± 1.48 69.0 ± 1.34
Hydrogen 3.2 ± 0.68 6.1 ± 0.64 2.8 ± 0.15 1.7 ± 0.23 1.3 ± 0.12 2.6 ± 0.22 1.3 ± 0.09 0.9 ± 0.15
Nitrogen 0.80 ± 0.12 1.00 ± 0.11 0.74 ± 0.05 0.64 ± 0.05 0.59 ± 0.06 0.92 ± 0.06 0.71 ± 0.04 0.52 ± 0.04
Sulphur 0.07 ± 0.01 0.05 ± 0.02 0.16 ± 0.01 0.14 ± 0.02 0.06 ± 0.02 0.08 ± 0.02 0.04 ± 0.01 0.01 ± 0.01
Oxygen 40.9 ± 1.94 37.6 ± 0.64 12.8 ± 1.21 9.1 ± 1.34 6.4 ± 1.80 11.1 ± 1.23 7.9 ± 1.51 5.3 ± 1.52
Elemental Ratios
H:C 0.89 1.78 0.52 0.30 0.23 0.48 0.23 0.16
O:C 0.71 0.68 0.15 0.10 0.07 0.13 0.09 0.06
(N+O):C 1.28 1.24 0.66 0.61 0.60 0.64 0.61 0.58
578 Values are means ± SEd

23
579 Table-2: Values of Freundlich isotherm models for urea adsorption onto rice straw and
580 husk biochars produced at different pyrolysis temperatures

Biochar KF n R2
RS 300 2.24 1.12 0.98**
RS 450 3.91 1.36 0.99**
RS 600 3.23 1.26 0.99**
RH 300 2.71 1.16 0.98**
RH 450 3.86 1.37 0.99**
RH 600 3.00 1.28 0.99**
581 Values are means
582 R2, the coefficient of determination
583 Credit Author Statement

584 Shiv Vendra Singh: Designed and performed the experiments, Analyzed the data, Wrote the
585 manuscript, Sumit Chaturvedi: Conceived research, Designed and performed the experiments,
586 Contributed to reagents/materials/analysis tools, Finalized the manuscript, V C Dhyani:
587 Designed and performed the experiments, Govindraju Kasivelu: Analyzed the data,
588 Contributed to reagents/materials/analysis tools.
589
590

591
592  Efficient utilization of rice derived carbonaceous material as adsorbent of nutrient
593 nitrogen.
594  Rice residue biochar had huge sorption potential of urea due to high functionality and
595 porosity.
596  Its predicted half-life was 500-750 years which varied positively with temperature
597  Sorption-desorption behaviour of rice residue biochar can be used to fabricate novel N
598 fertilizers.

599

24