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2020 - Ratio of H To C As Parameter To Predict Adsorption of Herbicides - Liu
2020 - Ratio of H To C As Parameter To Predict Adsorption of Herbicides - Liu
2020 - Ratio of H To C As Parameter To Predict Adsorption of Herbicides - Liu
Lan Wei, Yufen Huang, Lianxi Huang, Yanliang Li, Qing Huang, Guizhi Xu, Karin
Müller, Hailong Wang, Yong Sik Ok, Zhongzhen Liu
PII: S0013-9351(20)30217-6
DOI: https://doi.org/10.1016/j.envres.2020.109324
Reference: YENRS 109324
Please cite this article as: Wei, L., Huang, Y., Huang, L., Li, Y., Huang, Q., Xu, G., Müller, K., Wang, H.,
Ok, Y.S., Liu, Z., The ratio of H/C is a useful parameter to predict adsorption of the herbicide metolachlor
to biochars, Environmental Research (2020), doi: https://doi.org/10.1016/j.envres.2020.109324.
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2 Lan Wei: Data curation, Writing- Original draft preparation. Yufen Huang: Investigation, Data
3 Curation. Lianxi Huang: Investigation. Yanliang Li: Data Curation. Qing Huang: Investigation.
4 Guizhi Xu: Resources. Karin Müller: Writing- Reviewing and Editing. Hailong Wang: Supervision,
6
1 The ratio of H/C is a useful parameter to predict adsorption of the herbicide metolachlor to
2 biochars
3 Lan Weia,b,c , Yufen Huanga,b , Lianxi Huanga,b , Yanliang Lia,b , Qing Huanga,b , Guizhi Xua,b ,
a
5 Key Laboratory of Plant Nutrition and Fertilizer in South Region, Ministry of Agriculture, Institute of
7 510640, China
b
8 Guangdong Key Laboratory of Nutrient Cycling and Farmland Conservation, Institute of Agricultural
10 510640, China
c
11 Guangdong Key Laboratory of Integrated Agro-environmental Pollution Control and Management,
d
13 The New Zealand Institute for Plant & Food Research Limited, Ruakura Research Centre, Private
e
15 School of Environment and Chemical Engineering, Foshan University, Foshan, Guangdong 528000,
16 China
f
17 Key Laboratory of Soil Contamination Bioremediation of Zhejiang Province, Zhejiang A & F
24 1
25 Abstract Biochar adsorbent was produced by pyrolyzing traditional Chinese medicinal herb residue at
26 300, 500 and 750°C (referred to as biochar-300, biochar-500 and biochar-750). Basic physical and
27 chemical analyses, Fourier transform infrared spectroscopy (FT-IR), and thermodynamic analyses were
28 performed to elucidate adsorption and properties of biochar. Biochar adsorption capacity of herbicide
30 kg−1), followed the order: biochar-750 > biochar-300 > biochar-500. Thermodynamic analysis
31 suggested that adsorption of metolachlor on biochar was a spontaneous process. The adsorption
32 isotherm for the biochar produced at the highest pyrolysis temperature was characteristic for adsorption
33 process driven by a high surface area of biochar (85.30 m2 g−1), while the adsorption process for the
34 biochar produced at the lowest temperature was controlled by its higher content of organic matter
35 (39.06%) and abundant functional groups. The FT-IR spectra also showed that the biochar prepared at
36 the lowest temperature had the highest number of surface groups. In general, pore-filling induced by
37 the large surface area of the biochar was the dominant adsorption mechanism. When the H/C value was
38 >0.5, the adsorption mechanism of biochar was dominated by surface chemical bond, while pore-filling
40
41 Keywords: Chinese medicinal herb residue, Adsorption mechanism, Functional groups, pore-filling,
42 H/C ratio
43
46
47 2
48 1. Introduction
49 The annual waste generated by the traditional Chinese medicine industry, known as “herb residue”,
50 totals over 13 million tonnes in China (Wang et al., 2010b). Chinese medicinal herb residue is mainly
51 disposed of landfilling, stacking and incineration, which cause environmental problems. For example,
52 the waste liquid which comes from herb residue decomposed will pollute groundwater and rivers. On
53 the other hand the odor from the decomposition of herb residue can also lead to the regional ambient
54 air quality decrease (Wang et al., 2017). And the existing secondary utilization methods include
55 composting, cultivation of edible fungi, production of animal feed, production of biogas, and so on (Mi
56 and Yu, 2012). These methods have the disadvantages of low energy efficiency, high cost, many
57 by-products and difficult to store. Meanwhile, Large amounts of Chinese herbal medicine waste
58 (CHHMW) are treated as solid waste (Mi and Yu, 2016), representing a significant waste of cellulose,
59 hemicellulose, lignin and other nutrients contained in the herb residues. An environmentally friendly
60 procedure to recycle the solid herbal residual waste is, therefore, becoming an increasingly urgent
61 research topic.
62 Traditional Chinese medicine residue has high content of cellulose, hemicellulose and lignin, which
63 can be used as raw material of biochar. In addition, bio oil and gas obtained from the pyrolysis of
64 Chinese herbal residues can be used as renewable fuels. As a kind of biomass energy, traditional
65 Chinese medicine residue is a typical low carbon fuel. The main advantages are as follows: first, the
66 amount of greenhouse gas produced by the unit energy obtained during combustion is only about 1/8 of
67 the fossil energy; second, in terms of the whole life process of biomass energy (from the planting of
68 plants to the final incineration), the balance of "input" and "output" of biomass energy greenhouse gas
69 is so-called "carbon neutral". We think it is an environmentally friendly and economic way to prepare
3
70 biochar from Chinese medicine residue.
71 Biochar has recently been used as a soil amendment to enhance soil productivity (Dong et al., 2015;
72 Li et al., 2019), and mitigate climate change (Dong et al., 2013; Deng et al., 2017; Li et al., 2018). It is
73 also suggested as a sorbent for immobilization of potentially toxic elements (PTS) (Lu et al., 2014; Lu
74 et al., 2017; Qin et al., 2018; Yang et al., 2016; Yang et al., 2017) and organic contaminants (Zhang et
75 al., 2013; He et al., 2015) in the air (Zhang et al., 2019; He et al., 2018a), soil (Zhang et al., 2013; Xia
76 et al., 2019; Nie et al., 2018) and water (Niazi et al., 2018; EI-Naggar et al., 2019). Recent work has
77 reported a large surface area of biochar prepared from Chinese medicine waste materials, which
78 indicates that the material has a high sorption capacity for certain specific metals and organic
79 contaminants (Yang and Qiu, 2011; Shang et al., 2016). The sulfamethoxazole was effectively removed
80 by the biochar prepared from ‘Danshen’, which is a traditional Chinese medicine (Lian et al., 2014).
81 The authors suggested that biochar derived from herb residue may exhibit adsorption properties that are
82 distinct from those of biochars prepared from other raw materials in terms of abundant oxyl groups.
83 Cheng et al. (2012) suggested that much more active constituents including phenolic acids and
84 lipophilic tanshinones existed in the Chinese medicine herb (i.e., Danshen), compared with common
86 phytotoxicity, and chemical and microbial transformations and toxicity of heavy metals and organic
87 pollutants in soilsor sediments environments (Zhang et al., 2015), a clear understanding of the
88 mechanisms by which contaminants and biochar interact is required. To date, there are many studies
89 that investigate these mechanisms, but, in particular, the effect of pyrolysis temperature used for
90 producing herb residue biochar on adsorption of nonionic herbicides can make further efforts.
91 The main processes that affect the behavior of organic pollutants in the environment are adsorption,
4
92 degradation and movement. And adsorption is the most important one which will affect other processes
93 of pesticides (Müller et al., 2007). Adsorption kinetics is a key constituent to simulate the mobility,
94 availability and biological activity of organic pollutants in the environment (Selim 2003). It is an
95 economic and environmental feasible method to reduce the organic pollution in the environmental to
96 the minimum by immobilization and stabilization using biochar (Trakal et al., 2011). But biochar from
97 different raw materials also has different performance on pollutants when applied to soil. There are
98 many published studies which make the detailed explanation of an increase in pesticide adsorption and
99 decrease in dissipation with soil amended with biochar (Cao and Harris, 2012; Pignatello et al., 2017;
100 Xiao and Pignatello, 2015). However, Cabrera reported that soil amended with macadamia nut shells
101 biochar had little effect on increasing soil adsorbing herbicides (Cabrera et al., 2014). And another
102 report also found that addition of biochars did not increase the adsorption capacity of the soil for three
103 anionic compounds (Dechene et al., 2014). Therefore, it is necessary to select appropriate biochar as
104 adsorbent according to biochars’ properties and contaminants’ molecular structure for different
105 contaminant. It is not very clear what the most important influencing factors are and how they relate to
106 the adsorption mechanism. Lian and Xing summarized the molecular structure evolution of black
107 carbon during pyrolysis and the impact of biochar physicochemical properties on adsorption behavior,
108 stability, and potential risk (Lian and Xing, 2017). However, little is known about the microscopic
110 Existing literatures considered the adsorption mechanism on HOCs with biochar was a transition
111 from a partition dominant to an adsorption dominant process with increasing heat treatment
112 temperature (Lian et al., 2011; Chen et al., 2008). Lian and Xing (2017) elaborated the main
5
114 from different pyrolysis temperatures. Bornemann et al. (2007) reported that hole-filling adsorption
115 contributed significantly to the adsorption capacity of hydrophobic organic contaminants (HOCs) at
116 both relatively low and high concentrations. The development of different isotherm models, adsorption
117 mechanism and a comprehensive characterization of biochars can make the application more
118 accurately.
119 Previous literature shows that ratios of H/C and O/C were considered as indicators for the degree of
120 chemical composition and carbonization grade (Schimmelpfennig and Glaser, 2012; Hammes et al.,
121 2006). Kuhlbusch and Crutzen (1995) used element ratios to characterize biochar from vegetation fires
122 and suggested a H/C ratio of 0.2 to be suitable for defining black C. It was our objective to define
124 Previous researchers used various agricultural wastes as feedstocks for biochars. But there are few
125 studies on the preparation of biochar from Chinese medicinal herb residue. The method of biochar
126 preparation from Chinese medicinal herb residue was simple and the raw material is agricultural waste.
127 Moreover it could make full use of the abundant surface groups in herb residue to increase the
128 adsorption of pollutants (Qin et al., 2017). Biochars prepared from Chinese medicine residue are
129 available choices as a low cost sorbent to reduce agrochemical pollution and a best way of recycling
130 resources. Compared to another sorbent such as AC, the production of biochar is economical because
131 of the low energy demand and operation of a simple process without activation (Zhao et al., 2013).
132 This study, therefore, investigated the capability of herb residue biochars produced at different
133 pyrolysis temperatures to sorb the nonionic herbicide, metolachlor. We analyzed the relationship
134 between biochar properties and metolachlor adsorption capability and the effect of pyrolysis
135 temperature on adsorption. And the most important thing is to determine the role of H/C value in the
6
136 transformation of adsorption mechanism.
137
141 purity) was purchased from AccuStandard Incorporated (New Haven, Connecticut, USA). Other
142 analytical reagents chemicals were supplied by Guangzhou Chemical Company (Guangzhou, China).
143 Deionized water (18.2 MΩ cm) was produced using an ultrapure water system (EasyPure II RF/UV,
145
147 The biochar feedstocks were gathered from a Chinese medicine company in Huizhou. Among the
148 herbs used, the main ingredients were Codonopsis pilosula (Dangshen) and Angelica sinensis
149 (Danggui). The raw material was crushed into small pieces (sieved through a 0.9-mm polypropylene
150 mesh) and placed in a muffle furnace for pyrolysis. This was carried out in a nitrogen atmosphere at
151 three temperatures, namely 300, 500 and 750°C to produce biochar-300, biochar-500 and biochar-750
152 samples, respectively. The samples were heated to the respective maximum temperatures at a rate of 3–
153 6°C min−1 and then held at 300/500/750°C for 2 h to completely carbonize the herb residue. The
154 biochars were then sieved through a 0.5-mm polypropylene mesh. The method used by McLaughlin et
155 al. (2009) was used to evaluate the samples’ properties: moisture content was measured by heating in a
156 muffle furnace at 105°C for 24 h, mobile matter was determined by heating samples covered by a lid in
157 a furnace at 450°C; and the ash content was derived following heating the samples in air at 750°C for 1
7
158 h. Elemental composition (C, H, O, N and S) was measured by an elemental analyzer (Vario EL cube,
159 Elementar, Germany). The specific surface area was calculated by measuring N2 adsorption using a gas
160 adsorption analyzer (Quadrasorb ASIQMO002-2, USA) and the equation of Brunauer-Emmett-Teller
162
164 Batch equilibrium experiments were conducted in triplicate. Vials contained 0.05 to 0.1 g biochar,
165 10 ml of a buffer solution made of citric acid (10 m mol L-1), sodium dihydrogen phosphate (20 m mol
166 L-1) and NaN3 (200 mg L−1, pH 6.4), and nine metolachlor standards with concentrations ranging from
167 10 to 100 mg L−1. The control had the 10, 15, 20, 25, 30, 40, 60, 80 and 100 mg L−1 of metolachlor but
168 no biochar. There are three repetitions for all batch adsorption experiments.
169 The sample was placed in a brown 25-ml glass flask and sealed with a standard ground stopper.
170 After mixing solutes and adsorbents, the reactors were kept shaking at 180 rpm, 25°C for 24h to make
171 sure the adsorption reached equilibrium. The suspensions were filtered through 0.45-µm PTFE filter
172 after centrifuged at 4000 rpm for 25 min. The filtrate was collected and analyzed using
173 high-performance liquid chromatography. The mobile phase with a solvent mixture of water and
174 methanol with a ratio of 15:85 v/v at a flow rate of 1.0mL min-1 was used with an Xterra C18
175 reverse-phase column. The column temperature was set at 35°C, and a UV detector was applied at
176 230nm. The limit of detection was 7mg L-1, and the relative standard deviation was within 5% (Wei et
178
8
180 The following three models (Zhang et al., 2016) were used:
Qm ⋅ K L ⋅ Ce
182 Langmuir model: Qe =
(1 + K L ⋅ Ce )
S 0 ⋅ b ⋅ Ce
183 Dual-mode model: Qe = + K d ⋅ Ce
1 + b ⋅ Ce
184 Here, Qe and Ce represent, respectively, the equilibrium concentration of metolachlor in the solid
185 (mg kg−1) and liquid phase (mg L−1); Kf (mg1−n Ln kg−1) and KL (L mg−1) are the Freundlich and
186 Langmuir adsorption coefficients, respectively, and are indicative of the relative adsorption affinity and
187 adsorption energy; n is a parameter related to the linearity of the isotherm; Qm (mg kg−1) is the
188 Langmuir adsorption capacity; and Kd (L kg−1), So (mg kg−1) and b (L mg−1) are coefficients related to
189 surface adsorption (Kd is the dissolution domain partition coefficient, So is the number of adsorption
191
193 All the data were statistically analyzed using Microsoft Excel 2010 (Microcomputer Power, USA)
194 and SPSS18.0 (SPSS Inc., Chicago, IL, USA). A one-way analysis of variance and Duncan’s multiple
195 range tests at a 0.05 significance level were applied using SAS 9.0 (SAS Institute Inc., Cary, NC, USA).
196 All the figures were designed using Origin 8.0 (Origin Lab Corp., USA).
197
198 3. Results
200 The physico-chemical properties of the biochar samples are displayed in Table 1. The near-neutral
9
201 pH (7.44) observed for biochar-300 increased as the pyrolysis temperature increased; this was
202 attributed to the alkali salts which separated from organic matter (Shinogi and Kanri, 2003) and the
203 removal of surface acid activated groups (Ahmad et al., 2012) at higher pyrolysis temperatures. At the
204 same time, the content of mobile matter decreased with increasing pyrolysis temperature (from a
205 maximum of 39.1% for biochar-300), which may have been caused by the loss of organic matter, while
206 resident matter and ash content (57.7% for biochar-750) showed the opposite trend. These changes
207 were caused by a higher proportion of minerals and organic matter residue in the higher temperature
209 Results for the elemental composition, surface area and pore width, which together affect the
210 biochar’s pore-filling ability, are also shown in Table 1. The biochar-750 exhibited the highest surface
211 area (85.30 m2 g−1), pore volume (8.03×10-2 cm3 g−1) and carbon (C) content (79.09% in biochar-750,
212 3% and 20% higher than those of biochar-500 and biochar-300, respectively). Wang et al (2018) found
213 that the specific surface area of biochar produced from peanut shell, DTS/NK/KZ sludge, bamboo reed
214 and other raw materials at 300-700°C was in the range of 3.75-54.05 m2 g−1. In this experiment, the
215 specific surface area of biochar prepared from herb residue was in the range of 3.24-85.3 m2 g−1. It
216 means that when the preparation temperature was higher than 500°C, the specific surface area of
217 biochar-500 (54.28 m2 g−1) is larger than that of most other materials. On the contrary, the H, O and S
218 contents of the biochar decreased with increasing pyrolysis temperature. In fact, the S content was
219 below the instrument detection limit for the biochar-500 and biochar-750 samples. The N content
220 showed little change between a pyrolysis temperature of 300 to 500ºC but decreased to 1.5% for
221 biochar-750. Molar ratios were used to indicate the degree of aromaticity (H/C) and polarity (O/C,
222 (O+N)/C, (O+N+S)/C) with the magnitude of all of these ratios decreasing as the pyrolysis temperature
10
223 increased (Ahmd et al., 2012).
224
226 Fig. 1 shows that the three adsorption models fitted the experimental data well (r > 0.906), and
227 Table 2 presents the associated adsorption isotherm parameters and correlation coefficients. The
228 Freundlich adsorption coefficient Kf of 1208.31 mg1−nLn kg−1 was significantly higher for biochar-750
229 than for biochar-300 (322.12 mg1−nLn kg−1) and biochar-500 (319.53 mg1−nLn kg−1) (Fig. 1a). Indeed,
230 across the equilibrium solution concentration range, the amount of metolachlor sorbed was
231 significantly higher for the biochar-750 sample and lowest for the biochar-500 sample. For all samples,
232 the value of n (which decreases with increasing nonlinearity) was < 1 and decreased as the pyrolysis
233 temperature increased (reaching 0.247 for biochar-750). This trend was similar to findings reported by
235 The Langmuir adsorption coefficients KL and Qm were highest for the biochar-750 sample with KL
236 increasing with the pyrolysis temperature (Fig. 1b). For Qm the highest value observed was that for the
237 biochar-750 sample (3,092.32 mg kg−1), which was 89% higher than that of the biochar-500 sample
238 (1,633.67 mg kg−1) and 33% higher than the value for the biochar-300 sample (2,318.25 mg kg−1).
239 In the Dual-mode adsorption isotherm model the ratio (S0b)/Kd represents the intrinsic affinity of a
240 solute for the pore-filling domain relative to the dissolution domain for an infinite dilution case (He et
241 al., 2006). The highest value of (S0b)/Kd was observed for the biochar-750 sample (158.68) with a
242 decreasing trend with decreasing pyrolysis temperatures (Fig. 1c). The lowest value was found for the
243 biochar-300 sample (23.91). Notably, (S0b)/Kd has been reported as another measure of nonlinearity of
244 the adsorption isotherm, with higher values representing a more non-linear behavior (He et al., 2006).
11
245 Fig. 2 presents the metolachlor fractions that were removed from the solution by each of the biochar
246 samples across a range of metolachlor concentrations. It shows that with increasing initial metolachlor
247 concentrations the fraction of metolachlor removed from the solution decreased. The biochar-750
248 sample consistently removed the largest metolachlor fraction (between 91 and 34% depending on the
249 initial concentration), while little differences were observed between the biochar-300 (55–19%) and
251
253 As Fig. 3 shows, the change in Gibbs free energy (∆G) increased with an increase in the solid phase
254 equilibrium concentration of metolachlor. It seems that this factor controlled the reaction. Because ∆G
255 fell from −17.25 to −6.98 kJ mol−1, this indicated that the adsorption of metolachlor on the biochar
256 samples was thermodynamically favorable and endothermic process. Li et al. (2020) found that the
257 amount of tetracycline and Hg(II) removed by modified biochar increased as the solution temperature
258 increased from 25 to 45 ºC, which was consistent with our results.
259
261 The FTIR spectra of the three biochar samples before and after the metolachlor adsorption
262 experiments are presented in Fig. 4. For the unreacted biochar-300 sample (curve a1), the absorption at
263 3431 cm−1 corresponded to the stretching vibration of the –OH group of bonded water. Meanwhile, the
264 bands at 2997, 2922, 2869, 1436, and 1317 cm−1 were assumed to represent –CH2 and –CH3 stretching
265 vibrations (Chen et al., 2008; Hossain et al., 2011; Chen et al., 2005; Deng et al., 2019). The peaks at
266 1734, 1616, 1377 and 1512 cm−1 were attributed to C=O stretching of the ester bond, C=C and C=O to
12
267 stretching of the aromatic ring, plane bending of phenolic –OH related to ligneous syringyl units
268 (Keiluweit et al., 2010) and C=C ring stretching of lignin (Chen et al., 2008), respectively. According
269 to the literature, it was considered that the absorption peaks at 1616 cm-1 can be assigned to the
270 stretching vibration of C=C and C=O bonds of the quinonyl group (Habeeb et al., 2001). Keiluweit et
271 al. (2010) suggested that the adsorption at 781 cm−1 could be attributed to bending of an out-of-plane
272 aromatic –CH, and that adsorptions at 2360 and 2341 cm−1 indicates the stretching vibration of the
273 C≡C group. As the pyrolysis temperature was increased, the band intensities at 3400, 2869–2997, 1734
274 and 1616 cm−1 all decreased, with some disappearing completely for the biochar-750 sample, where
275 sharp peaks at 875 and 1145 cm−1 were instead observed. Changes in the FTIR spectra after the
276 metolachlor adsorption were observed indicating surface changes on the biochars (Fig. 4). After
277 sorbing metolachlor, it was found that small intensities decreased for all bands in the spectra for all
279
280 4. Discussion
281 Various mechanisms can explain the sorption phenomena including adsorption to the surface area,
282 hydrogen bonding, and absorption into the polymeric matrix (Huang et al., 2003). Previous studies
283 reported that the adsorption capacity between sorbents and non-ionic organic compounds depends on
284 its physical and chemical properties (Kim et al., 2012) and that the adsorption capability increases with
285 surface area (Mayakaduwa et al., 2016; Wang et al., 2010a; Yang et al., 2010). Various studies have
286 investigated the role of surface area and have shown that it might dominate adsorption mechanisms on
287 biochar (pore-filling) (Tan et al., 2015; Sun et al., 2016). But in our research, the adsorption capacity of
288 biochar-300 was higher than that of Biochar-500. This result was similar to the results reported by Lian
13
289 et al. (2014): Danshen biochar produced at 250°C showed 2 to 7 times higher adsorption capacity for
290 sulfamethoxazole (SMX) than biochar that was pyrolyzed at higher temperatures ranging between 400
291 and 800ºC. Biochar-300 contained the highest mobile matter (39.1%) of all samples. The degree of
292 mobile matter is related to the amount of organic matter, and therefore, decreased following the loss of
293 organic matter at higher temperatures (Ahmad et al., 2012). Considerable researches have also
294 indicated that the organic matter content is positive correlation between the adsorption capacity (Rojas
295 et al., 2013; Wilcke, 2000; He and Zhang et al., 2009; He et al., 2018b). For example, Rojas et al. (2013)
296 studied the capability of three unmodified organic residues and a soil to sorb six pesticides. They
297 reported that Kf increased with the sample’s organic matter content. Meanwhile, the atomic ratios of
298 H/C, O/C and (O + N)/C decreased with increasing pyrolysis temperature, indicating that the
299 low-temperature biochars contained more organic residues, such as polymeric CH2, lignin and cellulose
300 (Chen et al., 2008). Thus, one of the reasons for the increased adsorption may be that the higher organic
301 matter content in biochar-300 increased the number of adsorption sites. Infrared spectra also showed
302 that biochar-300 had more functional groups than biochar-500. Both acidic (carboxyl, lactonic,
303 carbonyl and phenolic) and basic oxygen-containing (ketone, pyrone and chromene) groups have been
304 found at the surface of biochar (Braida et al., 2003). The strong peaks observed at 3400, 2869–2997,
305 1734 and 1616 cm−1 involved the most active organic constituents and their residues (including
306 cellulose and lignin) and were preserved during the 300°C pyrolysis treatment, as corroborated by the
307 sample’s high oxygen content (27.2%). Biochars produced from Chinese traditional medicine had more
308 and stronger surface active groups especially quinonyl groups with the absorption peaks at 1664 cm-1
309 and 1631 cm-1 than biochars produced from another matetials. For example, the adsorption capacity of
310 herb residues biochar-300 (Kf: 322.12) was higher than that of rice husk biochar-300 (Kf: 148.19) (Wei
14
311 et al., 2017). Many of the active residues such as lipophilic tanshinones and phenolic acids have polar
312 sites with high-energy on the biochar surface if produced at low temperatures, which can sorb organic
313 compounds (Lian et al., 2014) or facilitate adsorption by preferentially sorbing water molecules and
314 polar adsorbates (Jia and Thomas, 2000) to form surface water clusters (Boehm, 2002). Biochar-300
315 showed the smallest variation of ∆G, which was in accordance with the findings of Lian et al. (2014)
316 who reported the lowest variation of ∆G values for a SMX sample prepared at 250°C, suggesting that
317 adsorption was more favorable and stronger than high-temperature biochars. The biochar-300 sample
318 also had more available adsorption points which can adsorb metolachlor, as confirmed by the analysis
320 Our research found that biochar-750 had the strongest adsorption capacity among all biochars
321 produced at different pyrolysis temperatures. This suggests that the adsorption mechanism was closely
322 related to the surface area of biochars. This report shows that increasing the pyrolysis temperature
323 increased the biochar’s surface area and total pore volume and decreased the pore width, in agreement
324 with that reported by Lian et al. (2014). In line with the large body of work demonstrating that a large
325 surface area and total pore volume of biochar play an important role on organic pollutants adsorption
326 (Chen et al., 2008; Ahmad et al., 2014), the present results show that the adsorption of metolachlor on
327 biochar prepared at a high pyrolysis temperature was driven by the biochar’s large surface area. Three
328 isotherm models were generally successful (r > 0.906) in describing metolachlor adsorption on
329 biochars prepared from herb residues at different pyrolysis temperatures. The Kf value of the
330 Freundlich model was lower than that observed for metolachlor adsorption on Eucalyptus wood
331 biochar (Graber et al., 2012). This difference may have been caused by the large specific surface area
332 of the wood biochar (242 m2 g−1). The same result was found in our previous study, where herb residue
15
333 biochars exhibited the higher adsorption capacity for metolachlor than rice husk biochars produced at
334 the same pyrolysis temperature (Wei et al., 2017). Surface areas of herb residue biochars were
335 1.58-2.95 times larger than those of rice husk biochars. Despite being well described by the Freundlich
336 and Dual-Mode models (r > 0.99), metolachlor adsorption to biochar-750 did not fit the Langmuir
337 equation well. The values of n (Freundlich) and (S0b)/Kd (Dual-Mode) also revealed that this sample
338 had the highest degree of nonlinearity. Xing and Pignatello (1997) suggested that smaller n values
339 represent broader energy distributions and, by inference, a greater contribution of the pore-filling
340 mechanism. This could imply that the adsorption mechanism for biochar produced under higher
341 pyrolysis temperatures may lead to a preference to pore-filling over partitioning (Luo et al., 2011). The
342 more negative ∆G value for biochar-750 indicates that adsorption was not governed by chemical
343 reactions. Luo et al. (2011) also considered that the combination of biochar with surface functional
344 groups was not the most important due to the negative ∆G.
345 The condensation process that turns amorphous carbon into crystalline carbon was evidenced by the
346 decrease in the H/C atomic ratio (Chun et al., 2004). The atomic ratio of H/C was an excellent mediate
347 index for reflecting the aromaticity of biochars and a perfect indicator for predicting the adsorption
348 capacity of organic contaminants on biochars (Xiao et al., 2016). Xiao et al. (2016) established a
349 quantitative relationship between H/C atomic ratio and aromatic structure, pyrolytic temperature. And
350 the most relationship between H/C value and adsorption properties for adsorbing naphthalene and
351 phenanthrene was revealed. As reported, H/C played an important role to declare a transitional
352 adsorption mechanism from chemical bond adsorption at low pyrolysis temperature to pore-filling at
353 high pyrolysis temperature. Chen et al. (2008) found that the H/C atomic ratio decreased with
354 increasing surface area, especially when the H/C value was 0.5, the specific surface area increased
16
355 significantly (from 19.92 to 112.4 m2 g−1). Sun et al. (2016) found a correlation between surface area
356 and aromaticity indicating that pore-filling in nanopores within aromatic C dominated nonlinear
357 propiconazole adsorption. In our study, H/C decreased from 0.87 (biochar-300) to 0.48 (biochar-500),
358 while the surface area increased at the same time from 3.24 to 54.28 m2 g-1. The adsorption mechanism
359 changed from surface chemical bond adsorption to pore-filling. We considered that when the value of
360 H/C was >0.5, the adsorption mechanism of biochar was dominated by surface chemical bond
361 adsorption. And in contrast, the pore-filling played a major role when the H/C value was 0.5. Fig. 5
362 summarizes the relationship between the ratio of H/C and pyrolysis temperature or mobile matter
363 respectively (Wu et al., 2012; Wei et al., 2017). When the H/C value was >0.5, the highest heat
364 temperature was always under 600 and the content of mobile matter was above 20%. Novak et al.
365 (2009) reported that the mobile matter content of biochars produced by pyrolyzing from pecan shells
366 and poultry litter at 700°C was reported to be in the range of 10-15%. The higher mobile matter content
367 was positive correlation with adsorption ability (Ahmad et al., 2014). Graham found that the effective
368 adsorbent surface of an activated carbon was controlled by pore volume and acid groups in the carbon
369 surface (Graham 1955). Previous studies (Fig. 6) show that when H/C value was 0.5 surface acid
370 groups were below 70 cmol kg-1. On the contrary, when the H/C value was>0.5, the amount of surface
371 acidic groups was positively correlated with the H/C value. So the surface active groups played a major
372 role in the adsorption when the value of H/C is greater than 0.5. Therefore the value of H/C can be a
373 mediate parameter to predict the structure-sorption mechanism. When the value of H/C was >0.5, the
374 adsorption mechanism of biochar was dominated by surface chemical bond adsorption such as
375 hydrophobic effect and π-bond. And in contrast, the pore-filling played a major role when the H/C
17
377
378 5. Conclusions
379 Three biochars were pyrolyzed from the herb residue of Chinese medicine, consisting mainly of
380 Dangshen and Danggui, at different temperatures in the range 300–750°C. This is an economical and
381 environmental procedure to pyrolyze Chinese medicine waste to biochar and use the product as sorbent
382 for organic contaminants. Increasing the pyrolysis temperature increased the pH, ash content, surface
383 area, pore volume and C content of the biochar while decreasing its mobile matter, O and H contents.
384 Three adsorption isotherm models, FITR and elements analysis were used to reveal the adsorption
385 mechanisms. The adsorption affinity of biochar to metolachlor for the biochar materials followed the
386 order: biochar- 750 > biochar-300 > biochar-500. Moreover, it was found that different adsorption
387 mechanism including pore-filling and polar functional groups contributed to the adsorption process.
388 For the biochar-750, the isotherm showed characteristics of an adsorption process based on large
389 surface area and a high total pore volume. For the biochar-300, a higher organic matter content with
390 more functional groups especially quinonyl groups was responsible for the higher adsorption of the
391 biochar pyrolyzed at the lowest temperature (300°C). For all Chinese traditional medicine-biochar, it
392 can be concluded that different adsorption mechanisms depended on the different heat treatment
393 temperature. Moreover, we propose that the value of H/C can potentially be an appropriate and
394 effective indicator to predict the adsorption mechanism of organic contaminants to biochars. When the
395 value of H/C was >0.5, the adsorption mechanism of biochar was dominated by surface chemical bond
396 adsorption, and when the H/C value was 0.5, the pore-filling mainly contributed to the metolachlor
397 adsorption.
398
18
399 Acknowledgments
400 This work was supported by Pearl River S&T Nova Program of Guangzhou, China (201610010131);
401 the National Natural Science Foundation of China (41401353, 41571313, 41807454, 21577131);
402 Natural Science Foundation of Guangdong Province, China (2015A030313570, 2016A030313772, and
405 Guangdong Academy of Agricultural Sciences, China (201716); Special fund for scientific innovation
407 R2016PY-JX006).
408
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29
1 Table 1
2 Physico-chemical properties of biochar pyrolyzed at three temperatures, namely at 300 (biochar-300), 500 (biochar-500) and 750°C
3 (biochar -750).
Moisture Mobile matter Resident matter Ash Surface area Pore volume Pore diameter
Biochar pH
(%) (%) (%) (%) (m2 g−1) (cm3 g−1) (nm)
biochar-300 7.44 2.39 39.06 9.10 49.46 3.24 1.16×10-2 3.93
biochar-500 9.65 2.29 29.70 13.31 54.70 54.28 5.34×10-2 3.74
biochar-750 9.75 2.51 24.95 14.89 57.65 85.30 8.03×10-2 3.47
4
1
6 Table 2
7 Parameters and correlation coefficients of three isothermal sorption models of metolachlor adsorbed to biochars pyrolyzed at three
8 temperatures, namely at 300 (biochar-300), 500 (biochar-500) and 750°C (biochar -750).a
9
Freundlich model Langmuir model Dual-mode model
Biochar Kfb n c
r d KL
e
Qm
f
rd Kd
g
S0
h
b
i
rd (S0b)/Kd
j
[(mg1-nLn )kg−1] (L mg−1) (mg/kg) (L kg−1) −1
(mg kg ) (L mg−1)
biochar-300 322.12±10.2** 0.455±0.006** 0.991** 0.047±0.001** 2318.25±16.32** 0.992** 5.12±0.025 1723.43±9.52** 0.071±0.001* 0.993** 23.91
** ** ** ** ** ** ** ** * **
biochar-500 319.53±9.5 0.349±0.008 0.996 0.082±0.003 1633.67±10.28 0.980 9.93±0.014 737.34±2.36 0.596±0.005 0.992 44.24
** ** ** ** ** ** ** ** **
biochar-750 1208.31±15.3 0.247±0.003 0.996 0.429±0.008 3092.32±3.25 0.906 25.48±0.074 1909.51±2.35 2.117±0.007 0.995 158.68
a
10 values are means ± SE
11 *correlation is significant at the 0.05 level (p<0.05)
12 **correlation is significant at the 0.01 level (p<0.01)
b
13 Kf is Freundlich constant indicating the sorption capacity.
c
14 n is Freundlich exponent that denotes the sorption isotherm curvature.
d
15 r is Pearson correlation coefficient.
e
16 KL is Langmuir constant indicating the sorption capacity.
f
17 Qm is Langmuir sorption capacity.
g
18 Kd is Dual-mode coefficient which is the dissolution domain partition coefficient.
h 0
19 S is Dual-mode coefficient which is number of adsorption sites per mass of sorbent.
i
20 b is Dual-mode adsorption constant.
j 0
21 (S b)/Kd is intrinsic affinity of solute for the hole-filling domain relative to the dissolution domain given infinite dilution.
2
22
3
4200
biochar-300 3500 biochar-300
(a) (b)
biochar-500 biochar-500
3500
biochar-750 biochar-750
2800
2800
2100
Qe (mg kg )
Qe (mg kg )
-1
-1
2100
1400
1400
700
700
0 0
0 20 40 60 80 100 0 20 40 60 80 100
-1 -1
Equlibrium Concentration (mg L ) Equlibrium Concentration (mg L )
4200
biochar-300
(c)
biochar-500
3500
biochar-750
2800
Qe (mg kg )
-1
2100
1400
700
0 20 40 60 80 100
-1
Equlibrium Concentration (mg L )
2
3 Fig. 1. Sorption isotherm for metolachlor to Chinese medicine residue derived
4 biochars produced at different pyrolysis temperatures (300°C, biochar-300; 500°C,
5 biochar-500 and 750°C, biochar-750). a: Freundlich equilibrium isotherm; b:
6 Langmuir equilibrium isotherm; c: Dual-mode equilibrium isotherm.Qe is the solid
7 phase equilibrium concentration (mg kg-1). (T = 25 °C).
8 Qe is the solid phase equilibrium concentration (mg kg-1).
1
100
biochar-300
biochar-500
80 biochar-750
60
Removal(%)
40
20
0
0 20 40 60 80 100
-1
Intial Concentration (mg L )
10
11 Fig. 2. Percentage removal of metolachlor from solution by biochars pyrolyzed at
12 three temperatures (300°C, biochar-300; 500°C, biochar-500 and 750°C,
13 biochar-750).
2
-6
(b) 25
-8
-10
∆ G (kJ/mol)
-12
-14
biochar-300
biochar-500
-16 biochar-750
14
15 Fig. 3. Gibbs free energy change (∆G) of metolachlor adsorbed by herb residue
16 biochars pyrolyzed at three temperatures (300°C, biochar-300; 500°C, biochar-500
17 and 750°C, biochar-750) (T = 25 °C).
18
3
19
20
21 Fig. 4. FT-IR spectra of biochars pyrolyzed at three temperatures (300°C,
22 biochar-300; 500°C, biochar-500 and 750°C, biochar-750) (a1, b1, c1: before
23 adsorption reaction; a2, b2, c2: after adsorption reaction).
4
1000
a
800
600
HHT
400
200
0
0 0.5 1 1.5 2 2.5 3
H/C
24
100
b
80 y = 38.571x + 2.8246
2
R = 0.7259
Mobile matter %
60
40
20
0
0 0.4 0.8 1.2 1.6 2
H/C
25
26 Fig. 5. Comparison of hydrogen to carbon (H/C) molar ratio versus the Highest
27 Heating Temperature (HHT) (a) or mobile matter (%) for the biochars produced at
28 different pyrolysis temperatures (Data form Ahamd et al., 2014).
5
250
200
Acid groups (cmol kg )
-1
150
100
50
0
0 0.2 0.4 0.6 0.8 1
H/C
29
30 Fig. 6. Correlation of the acid groups (cmol kg-1) and the hydrogen to carbon (H/C)
31 molar ratio for the biochars produced at different pyrolysis temperatures (Data from
32 Wu et al., 2012; Wei et al., 2017).
33
6
1 There is a new way of treating herb residues as a recycled raw material.
2 The H/C value of biochar can be used to predict the metolachlor adsorption
3 mechanism.
4 The sorption affinity of biochar to metolachlor for the samples was Biochar-300 >
5 Biochar-500.
6 The pore-filling and polar functional groups on the biochar surfaces are the main
7 factor affecting adsorption of low temperature biochar.