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Yingjie Dai, Qiya Sun, Wensi Wang, Lu Lu, Mei Liu, Jingjing Li, Shengshu Yang, Yue
Sun, Kexin Zhang, Jiayi Xu, Wenlei Zheng, Zhaoyue Hu, Yahan Yang, Yuewen Gao,
Yanjun Chen, Xu Zhang, Feng Gao, Ying Zhang
PII: S0045-6535(18)31254-2
DOI: 10.1016/j.chemosphere.2018.06.179
Reference: CHEM 21711
Please cite this article as: Dai, Y., Sun, Q., Wang, W., Lu, L., Liu, M., Li, J., Yang, S., Sun, Y., Zhang,
K., Xu, J., Zheng, W., Hu, Z., Yang, Y., Gao, Y., Chen, Y., Zhang, X., Gao, F., Zhang, Y., Utilizations of
agricultural waste as adsorbent for the removal of contaminants: A review, Chemosphere (2018), doi:
10.1016/j.chemosphere.2018.06.179.
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4 Yingjie Dai Qiya Sun, Wensi Wang, Lu Lu, Mei Liu, Jingjing Li, Shengshu Yang,
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5 Yue Sun, Kexin Zhang, Jiayi Xu, Wenlei Zheng, Zhaoyue Hu, Yahan Yang, Yuewen Gao,
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6 Yanjun Chen, Xu Zhang, Feng Gao and Ying Zhang*
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9 University, No.600 Changjiang Road, Xiangfang District, Harbin 150030, China
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11 Abstract
12 In recent years, various industrial activities have caused serious pollution to the environment. Due to the
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13 low operating costs and high flexibility, adsorption is considered as one of the most effective technologies for
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14 pollutant management. Agricultural waste has loose and porous structures, and contains functional groups
15 such as the carboxyl group and hydroxyl group, so it can be invoked as biological adsorption material.
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16 Agricultural waste gets the advantages of a wide range of sources, low cost, and renewable. It has a good
17 prospect for the comprehensive utilization of resources when used for environmental pollution control. This
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18 article summarized the current research status of agricultural waste in adsorbing pollutants, which pointed out
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19 the influencing factors of adsorption, expounded the adsorption mechanism of biological adsorption and
20 introduced the related parameters of adsorption, proposed the application of adsorbents in engineering
21 including adsorption in liquid and gas phases, at the same time it gave the future development prospect of
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26 *Corresponding author. Tel.: +86 451 5519 0993; Fax: +86 451 5519 0993.
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30 Contents
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31 1. Introduction ...................................................................................................................................................... 3
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32 2. Types, structures and resource utilization of agricultural waste ....................................................................... 6
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33 2.1. Types and structures of agricultural wastes ........................................................................................... 6
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49 4.2.1. Antibiotics................................................................................................................................. 18
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50 4.2.2. Other Drugs .............................................................................................................................. 19
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51 4.3. Pesticides ............................................................................................................................................. 20
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4.5. Oil substances ...................................................................................................................................... 22
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54 4.6. Adsorption mechanisms for organic pollutant removal ....................................................................... 23
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59 7. Adsorbent regeneration................................................................................................................................... 27
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61 9. Conclusions .................................................................................................................................................... 29
62 Acknowledgement .............................................................................................................................................. 30
63 References .......................................................................................................................................................... 30
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65 1. Introduction
66 Agricultural waste is a general term for organic substances discarded by human beings in the process of
67 agricultural production. It mainly includes plant waste, livestock and poultry manure, agricultural and sideline
68 products processing waste, rural household waste (Wang et al., 2016). Agricultural waste, which originates
69 from our life, mainly refers to crop stalks and animal manure (Liu, 2017). It is characterized by a wide range
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70 of sources, large quantity, reproducible, biodegradable and environmental-friendly. Research showed that the
71 total agricultural wastes in 2013 was 1.75×109 tons in China, of which crop straw was 9.93×108 tons,
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72 accounting for 56.82%, livestock and poultry manure was 4.52×108 tons, accounting for 25.85%, forest
73 residues were 3.03×108 tons, accounting for 17.33% (Zuo, 2015). Fig. 1 shows the proportion of agricultural
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74 wastes. In addition, with the rapid development of social economy and the increase of population, total waste
75 production will increase at a rate of 5% to 10% a year and the annual output of waste is estimated to exceed
78 pollution has caused serious harm to human health, so it is urgent to solve ecological problems. Conventional
79 methods for removing contaminants from gaseous and aqueous phases are mainly biological treatment,
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80 flocculation (Jawad et al., 2015), membrane separation processes, chemical precipitation, adsorption (utilizing
81 activated carbon) and ion exchange (Rosales et al., 2017). Among these methods, adsorption has been shown
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82 to be an effective and cost-effective method for removing many pollutants (Ashrafi et al., 2015). In adsorbents,
83 activated carbon adsorption is an effective and reliable method. Activated carbon has the benefits of high
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84 surface area, micro-porous structure, uniform pore size distribution, high porosity, high surface reactivity,
85 superior mechanical strength and strong adsorption capacity (Mashhadi et al., 2016). However, the high cost
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86 of this approach has prompted the search for alternative industries (Jawad et al., 2015). Agricultural waste has
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87 a loose, porous structure and contains carboxyl, hydroxyl and other reactive groups, can be used as a biomass
88 adsorption material in the field of pollution control, which can not only reduce the environmental burden but
89 also achieve the effect of "treating waste by waste" (Huang, 2017). The agricultural wastes used for distortion
90 mainly include straw (Salem and Yakoot, 2016), wheat straw (Shang et al., 2015), bagasse (Rattanachueskul et
91 al., 2016), banana skin (Gupta and Gupta, 2015), walnut shell (Tonucci et al., 2015), coconut shell (Tang et al.,
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92 2017), avocado skin (Marahel et al., 2013; Palma et al., 2016), olive powder (Gámiz et al., 2016;
93 López-Cabeza et al., 2017; Peña et al., 2016), mustard (Safa, 2016; Trivedi et al., 2016), linen (Safa, 2016;
94 Sharma et al, 2016), cucumber (Lee et al., 2015; Smitha et al., 2012), waste tea (Zhou et al., 2015), earthworm
96 At present, a great deal of researches has been made at home and abroad on taking advantage of agricultural
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97 wastes as biomass adsorbents for the treatment of pollutants. Numerous researchers have done a lot of
98 research on the use of agricultural waste to adsorb heavy metals. Salmania et al. (2017) studied the removal of
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99 cadmium ions by magnetized biochar based on orange peel and conventional orange peel (Salmania et al.,
100 2017). Houda and Moussa (2017) studied that using banana waste to remove zinc ions from aqueous solutions.
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101 In addition, many researchers studied to remove extra dense metal (Houda and Moussa, 2017). In organic
102 adsorption, Djelloul and Hamdaoui (2015) researched the kinetic adsorption of methylene blue (MB) by
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melon peel in packed columns (Djelloul and Hamdaoui, 2015). Shang et al. (2015) studied the use of
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104 thermally activated pinecone as a low cost adsorbent to remove dimethyl trisulfide from aqueous solutions
105 (Shang et al., 2015). Currently adsorption has been successfully employed to remove inorganic, organic
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106 pollutants and gases in the environment. However, research on gas is comparatively fewer.
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107 In recent years, a great deal of agricultural waste has been generated every year around the world. At
108 present, extensive agricultural waste disposal methods not only fail to effectively convert and utilize
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109 agricultural resources, but also cause serious environmental pollution. A large amount of N2O, SO2, CH4 and
110 smoke are generated during the process of fecal burning and rice straw incineration, which seriously pollutes
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111 the atmosphere (Wei, 2013). In addition to organic matter in livestock and poultry manure, there are mass
112 pathogenic bacteria, parasitic eggs and heavy metal (Zhang and Wu, 2016). They are given directly into the
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113 water without proper treatment, causing serious contamination of groundwater and surface water systems (Wei,
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114 2013). Traditional organic fertilizers have been gradually superseded by chemical fertilizers and other
115 chemical materials, due to the widespread use of pesticides. Fertilizers greatly narrows the quality of the soil
116 and the soil buffer capacity. Therefore, improving the reuse of agricultural wastes could effectively replenish
117 soil nutrients enhances the quality of arable land (Liu, 2017). In the face of agricultural waste and ecological
118 environmental damage caused by agricultural waste, researching on the utilization of agricultural waste has
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119 caused widespread concern. The rationalization of agricultural wastes is of profound significance to
120 effectively alleviate the environmental pollution and improve the ecological environment.
121 In order to comprehend the research progress of agricultural wastes as adsorbents, this paper reviews the
122 literature in recent years. At present, Zhou et al. (2015) reviewed the removal of organic pollutants on
123 agricultural wastes. Nguyen et al. (2013) summarized the removal of heavy metals from water using
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124 agricultural waste. Rosales et al. (2017) reviewed the development of biochar as a low cost adsorbent.
125 However, there was not any comprehensive review on the application (remove organic, inorganic and gas) of
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126 agricultural waste as adsorbent. The main purpose of this paper was to present a summary of the latest
127 information on the use of agricultural waste as an adsorbent in environmental management (see Fig. 2). The
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128 article (i) introduced the mechanism of removing inorganic (heavy metals, N and P), organic matter (dyes,
129 drugs, pesticides, aromatic compounds, and oil substances) and gases respectively; (ii) listed the adsorption
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parameters of typical agricultural wastes under the experimental conditions; (iii) analyzed the factors affecting
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131 the adsorption process; (iv) made a forecast on the future development of agricultural waste.
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135 Agricultural wastes are lignocellulosic materials and the main structural components are lignin, cellulose
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136 and hemicellulose (Salleh et al., 2011). Lignin is only an aromatic polymer, which consists of carbonyl,
137 hydroxyl, methyl and other functional groups. Both hemicellulose and cellulose contain oxygen functional
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138 groups including carbonyl groups, hydroxyl groups and ether. These functional groups can bind heavy metal
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139 ions and organic small molecule contaminants by cheating, completing, coordinating, hydrogen bonding and
140 the like, which play an important part in the preparation of adsorbents (Zhou et al., 2015). Chemical
141 composition analysis of conventional agricultural wastes is presented in Fig. 3. When agricultural waste
142 absorbed heavy metal ions, the dynamic functional groups took an important role, in which O element can
143 form coordination bonds with heavy metals (Wen et al., 2017). The focal mechanism, by which agricultural
144 wastes adsorb dyes was generally influenced by several processes (Shah et al., 2016). In general, agricultural
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145 waste directly acts as an adsorbent and researchers are now paying much attention to increase the adsorption
146 capacity of cultivated waste through modification (chemical and physical). Ashrafi et al. (2015) optimized
147 adsorption conditions for basic blue 41 based on the Box-Behnken design response surface methodology
148 using NaOH-modified rice husk. It is shown that the method of NaOH modification can be used to improve
149 the rice husk to raise the adsorption capacity (Ashrafi et al., 2015). Abdelwahab et al. (2016) separated the oil
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150 from water through polymer coated partially esterified sugarcane bagasse (Abdelwahab et al., 2016). In
151 general, modification can improve the adsorption capacity of agricultural wastes.
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152
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153 2.2. The resource utilization of agricultural waste
154 Agricultural waste is highly available and is utilized in a variety of ways. At present, there are mostly five
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aspects of resource utilization of agricultural waste. Fertilizer utilization, making the waste into fertilizer and
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156 soil conditioner by using agricultural waste fertilizer technology, which can lead to the return of organic
157 fertilizer to the soil, increase the organic content of the soil, ensure the organic minerals need for the growth of
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158 the plant, improve the soil structure and reduce the application of chemical fertilizers and pesticides (Deng,
159 2017). Feed utilization, using the crop straws as feed, which will help animal digestion and absorption. It can
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160 largely curb the burning of straw and reduce greenhouse gas emissions. The industrialization and construction
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161 raw materials of agricultural waste mean that is used as a raw material for paper making and the output of
162 polymer panels instead of wood. Energy utilization of agricultural wastes mainly includes anaerobic
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163 fermentation and direct pyrolysis. Converting agricultural waste into electricity is direct combustion pyrolysis.
164 It largely contained open-air straw burning and coal combustion. So it can hold back the occurrence of acid
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165 rain, to a certain extent. Optimization is utilizing the proper treatment of agricultural waste as a substrate
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166 material for mushrooms, vegetables production (Chen and Shi, 2017). In addition, agricultural waste is a
167 natural, environmental and economic adsorbent source. Because of its loose surface, porous, superior
168 mechanical strength and chemical stability, it is appropriate for the restoration of ecological pollution.
169 However, there is poorly researched on agricultural wastes as adsorbents at present, so it is of great
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174 The rapid advance of industrialization and rapid urbanization has resulted in the excessive discharge of
175 heavy metal-containing wastewater into the environment, seriously affecting human health (Zhang et al.,
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176 2016). These metallic elements have been defined as mutagenic and carcinogenic agents, and may be toxic to
177 aquatic life (EPA, 2017). Over decades, numerous cadmium remediation techniques, broadly classified into
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178 chemical precipitation, flotation, ion exchange, adsorption and membrane filtration, have been established for
179 cadmium removal (Kurniawan et al., 2006; Pehlivan and Altun, 2006). These methods have significant
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180 disadvantages, including elevated energy requirements, incomplete metal removal, generation of toxic sludge,
181 demanding treatment and expensive equipment (Farhan et al., 2012). In this context, proscription has proved
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182 to be a promising method, with such benefits as: (1) the minimization of chemical sludge; (2) low cost of
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183 promotion and without detrimental effects on the environment (Du et al., 2016). Fig. 4 accurately describes
184 the mechanisms of adsorption of heavy metal ions in agricultural wastes including chemical adsorption,
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185 physical adsorption, ion exchange, membrane diffusion, particle diffusion, chelation, electrostatic attraction,
186 surface complexation, ligand exchange and internal complexation. An increasing number of studies have
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187 shown that agricultural waste can contribute to immobilization of heavy metals (Qian and Chen, 2013; Qian et
188 al., 2016). This section will describe in the adsorption of several archetypal heavy metal ions by agricultural
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189 waste.
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192 Lead is detrimental heavy metal to the body. Lead and its compounds enter the body that will do harm to
193 the nervous, cardiovascular, hematopoietic, kidney, digestive and endocrine and other systems. If the content
194 is overproof, it will cause lead poisoning. With the rapid progress of the industrial market, lead has been
195 widely used in all walks of life. Simultaneously, it causes environmental pollution and health hazards to the
196 human body. At present, lead affects human health mainly through food, drinking water, air and other
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198 in drinking water is 15.00×10-3 mg/L (EPA, 2017). Amer et al. (2017) has been established that rice husk was
199 an efficient adsorbent for adsorbing Pb (II) in experiments (Amer et al., 2017). The disruption was due to
200 multiple mechanisms: Surface complexation with carboxylic and hydroxyl functional groups, ion exchange
201 with Ca (II), Mg (II), and physical forces of attraction. They found the benefits of rice husk as an adsorbent.
202 Pb (II) can be marked by using an acid and eventually recovered. Rice straw can be regenerated for a certain
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203 number of cycles. So the resources can be stored. El-Deen and El-Deen (2016) did some experiments and
204 found the phosphoric acid activated coconut shell (ACS) adsorbed more Pb (II) than inactivated coconut shell
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205 (CS) (El-Deen and El-Deen, 2016). They operated a series of adsorption experiments to measure the use of the
206 ACS as a dissolution agent for the absorption of lead in wastewater and to compare it with pyrolysis of CS.
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207 The results demonstrate that the biological adsorbent (ACS) is under a high surface area and functional groups.
208 Table 1 shows the adsorption of lead by other agricultural wastes. As can be seen from the figure, there are
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209 many kinds of agricultural wastes that can absorb lead ions, which is a method worthy of being promoted to
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210 handle heavy metal ion pollution.
211
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213 Cadmium (Cd) is seen as an extremely toxic metal without a known biological function (Wang et al., 2010).
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214 Cadmium accumulates in the human body, especially in the kidneys and it can lead to insufficiency of renal
215 function. Being dependent on the World Health Organization and its recommended standard values, the
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216 permissible limit of cadmium in drinking water was 0.005 mg/L. Cadmium is widely used in various kinds of
217 industrial activities (e.g., pigment manufacture, refining of non-ferrous metals), and the subsequent release of
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218 cadmium-containing wastewater into the environment has become a focus of global concern over the past
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219 years, due to its high toxicity, environmental accumulation and non-biodegradable characteristic (Park et al.,
220 2017). Gondhalekar and Shukla (2015) studied the principal mechanism for Cd (II) removal utilizing raw
221 walnut shell was ion exchange (Gondhalekar and Shukla, 2015). Because the ester and acetyl operative groups
222 have been changed to carboxylate, the ability of dissolution increased. Singha and Guleria (2014) used
223 succinylated cellulosic biomass as adsorbent to remove heavy metal ions (Singha and Guleria, 2014). Studies
224 have found that ion exchange is the main mechanism. The possible mechanism is shown in Fig. 5. Two
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225 adjacent carboxyl and hydroxyl groups are attached by a divalent heavy metal ion, and two pairs of electrons
226 can be given to the metal ion to form four coordination number compounds and release the two sodium ions
227 and protons into the solution. Farasati et al. (2015) compared the adsorption ability of Phragmites australis (P.
228 australis) with sugarcane stalks on cadmium ions (Farasati et al., 2015). They discovered the reason why
229 sugarcane stalks adsorbed more Cd (II) than P. australis were the most extended surface area and softer
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230 surface. Chen et al. (2015a) evaluated biochar derived from geophysical dried sewage sludge through
231 pyrolysis at 1173K (Chen et al., 2015a). The results showed a minimal contribution of organic matters on
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232 cadmium removal whereas alkaline earth metals such as calcium was in charge of the adsorption process
233 owing to cation exchange and surface precipitation by the formation of insoluble cadmium salt under alkaline
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234 conditions. In addition, there is ample data in Table 2 indicating that agricultural waste can absorb cadmium as
235 an adsorbent. Consequently, agricultural waste will be a popular cheap adsorption in the future according to its
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236 non-pollution exchange progress and high removal rate. At present, there is less research on cadmium ion
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237 adsorption in agricultural waste, and more research is needed.
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240 Copper and its alloys (brass and bronze) have been used in ordinary household wiring, photovoltaic cells
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241 and phytotherapy products as fungicides, fertilizers, algicides and insecticides. The EPA has set the acceptable
242 limit of copper in drinking water at 1.30 mg/L. Table 3 shows manifold groups of cultivated waste adsorbed
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243 copper ion data. Removal of Cu (II) from aqueous solution via adsorption has been extensively employed in
244 the wastewater treatment plant (Jin et al., 2016). When a large amount of dense metal remains in the human
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245 body, it is not hard to make the body's organs heavy burden especially the liver and gall bladder. When these
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246 two organs appeared problems, the body's metabolism would be frightened. Guechi et al. (2015) studied the
247 adsorption of copper ions by potato peel (PP) (Guechi et al., 2015). They found that the adsorption kinetics
248 absorption of Cu (II) at different initial metal ions was analyzed by pseudo level, pseudo two levels and
249 particle internal diffusion model. It was pointed out that the maximum adsorption capacity (qm) was 84.74
250 mg/g at 298K. The thermodynamic parameters of Cu (II) adsorption on PP were also calculated. The results
251 showed that PP was a type of adsorbent suitable for removing Cu (II) from aqueous solution. Mokkapati et al.
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252 (2016) also studied difference among three kinds of agricultural waste (banana stem powder, casuarinas fruit
253 powder, sorghum stem powder) (Mokkapati et al., 2016). They did a lot of experiments to study the impact of
254 different factors on the adsorption effect. The qm for the three adsorbents for Cu (II) was 6.50 mg/g, 4.50 mg/g
255 and 7.90 mg/g, respectively. The mechanism of banana stem powder and casuarinas fruit powder is
256 chemisorptions, and the mechanism of sorghum stem powder is the combination of both physisorption and
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257 chemical attachment. So they affirmed the three adsorbents could remove Cu (II) from aqueous environment.
258
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259 3.1.4. Nickel
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260 Nickel is the human body essential life element, and in the human body content is extremely tiny. Under
261 normal circumstances, the human body contains the nickel to 10.00mg and the blood normal concentration is
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0.11 mg/L. Nickel is also the most widespread sensitization of metal. Nickel ions can penetrate through the
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263 pores and sebaceous glands inside the skin, leading to allergic inflammation of the skin. Once into
264 sensitization symptoms, nickel allergy can be indefinitely sustained. More worrying thing is the poisoning
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265 resulted from excessive intake of nickel. The mortal body is daily intake of soluble nickel 250.00mg will
266 cause poisoning. And the peculiar symptoms are dermatitis, respiratory disorders and respiratory tract cancer
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267 (http://baike.asianmetal.cn/metal/ni/health.shtml). Many experiments in Table 4 showed that nickel ions could
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268 be absorbed by a variety of agricultural wastes. Singh and Shukla (2017) proved that the waste citrus limits
269 peel was a cheap and abundantly available biomass, which showed excellent potential for adsorbing Ni (II)
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270 (Singh and Shukla, 2017). Ion exchange mechanism was involved in dissolution which receives the support of
271 FTIR, isotherm and desorption studies. Under the most suitable physical and chemical conditions, qm was
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272 27.78 mg/g. Desorption studies using HCl showed almost complete recovery of Ni (II) ions. Hence, citrus
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273 limits peels owing to its porous structure, high sorption rate, low cost, and comparatively high uptake capacity
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277 In addition to the above mentioned abundant heavy metal ions, there are many other heavy metal ions that
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278 can also have an influence on human health, for example, Mercury has chronic toxicity to human. Song et al.
279 (2015) found rice husk and rice straw could absorb Hg (II) by ion exchange (Song et al., 2015). Chromium
280 can cause dermatitis, eczema, bronchitis and rhinitis, causing allergic reactions and carcinogenic effects. Ding
281 et al. (2016) conducted a series of experiments and found that the rice husk had the qm of rice husk for Cr (VI)
282 adsorption was 18.20 mg/g at pH 6.0 and room temperature. Too much zinc can cause poisoning, for example,
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283 excessive intake of zinc can cause acute zinc poisoning, vomiting, diarrhea and other gastrointestinal
284 symptoms, chronic zinc poisoning may have anemia and other symptoms (Ding et al., 2016). Najam and
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285 Andrabi (2016) using experimental data showed that the walnut shell adsorbed Zn (II) through the mechanism
286 of ion exchange (Najam and Andrabi, 2016). Table 5 and Table 6 shows in the adsorption of metal ions by
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287 multiple sets of data. However, there becomes less research on these kinds of heavy metal ions in agricultural
288 wastes, and the research on these metals can be deepened in the future.
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290 3.2. Nitrogen and Phosphorus
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291 Agricultural waste cannot be only adsorb heavy metal, but also adsorb nitrogen and phosphorus (NO3-,
292 PO43-, NH4+-N). This section summarizes the data on the adsorption of Nitrogen and phosphorus from
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293 agricultural wastes through the literature search in Table 7. Generally, the surfaces of most carbon-rich and
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294 low-mineral biochars are negatively charged and have little or no ability to delete anions, particularly PO43-
295 (Jung et al., 2015; Yao et al., 2011). For example, Kizito et al. (2015) has studied wood and rice husk
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296 adsorption of ammonium ions in NH4Cl solution and slurry solutions (Kizito et al., 2015). It was noted that
297 the adsorption effect was accomplished in the case of chemisorption and physisorption, and qm reached 133.33
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298 mg/g, 78.06 mg/g, 71.94 mg/g and 59.56 mg/g, respectively. In addition, Zhu et al. (2016) studied the avocado
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299 seed at 298K, pH of 5.0 by an ion exchange mechanism reached the gm of 5.40 mg/g (Zhu et al., 2016). Jung
300 et al. (2015) discovered that biochars derived from soybean stover, bamboo wood, and maize residue showed
301 no sorption capacity for PO43- removal and even released inherent PO43- into the solution (Jung et al., 2015).
302 Nguyen et al. (2015) modified to study the adsorption of zirconium loaded Okara to PO43-, and the
303 experimental results showed that at room temperature, when zirconium loaded okara in acidic environment
304 with pH of 3.0, its qm was 16.43 mg/g (Nguyen et al., 2015). In short, agricultural waste can absorb N and P,
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305 through chemisorption and physisorption, ion exchange mechanism, and the enriched bio-carbon obtained
306 after adsorption can be used as slow-release fertilizer for horticulture and agriculture (Nguyen et al., 2015).
307
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309 In recent years, with the continuous use of emerging organic products, it has caused pollution problems
310 such as water and soil. At present, the application of agricultural waste as adsorbent in water and soil to
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311 remove all kinds of organic pollutants has been a great effort. Among them, the studies of pollutants are
312 mainly dyes (methylene blue (MB), rhodamine B, crystal violet, malachite green, Congo red) (Chebli et al.,
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313 2015; Feng et al., 2015; Nayak and Pal, 2017; Ren et al., 2016; Smitha et al., 2012; Wang et al., 2017), drugs
314 (tetracycline, caffeine, tylosin) (Chen et al., 2016; Portinho et al., 2017; Yin et al., 2016), pesticides (metalaxyl,
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metribuzin, 2,4-dichlorophenoxyacetic acid) (Gámiz et al., 2016; Peña et al., 2016; Trivedi et al., 2016),
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316 aromatic compounds (polycyclic aromatic hydrocarbons, phenol) (Gupta and Gupta, 2015; Karri et al., 2017)
317 and oil substances (emulsified oil, diesel oil, lubricating oil) (Abdelwahab et al., 2016; Chai et al., 2015;
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319 A number of treatment techniques have been developed to remove organics, such as flocculation (Guan and
320 Tian, 2017), sedimentation (Wen et al., 2017), light treatment (Deng et al., 2017), membrane processes
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321 (Sarasidis et al., 2017), chemical oxidant oxidation (Gayathri et al., 2017), biological oxidation (Chen et al.,
322 2017), photo-catalytic oxidation/degradation (Janssens et al., 2017), adsorption (Huang et al., 2017) and
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323 combined methods (Sandoval et al., 2017; Zhou et al., 2015). Among them, adsorption is the most concerned
324 because of its high removal rate and simple operation. However, conventional adsorbents such as activated
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325 carbon are cost-effective, and it is not economically viable to achieve their widespread use in the removal of
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326 organic contaminants. Therefore, the bio-adsorbent prepared by theunassuming, easy and low-cost agricultural
327 waste has become the focus of the researchers. At present, various biosorbents prepared from agricultural
328 waste can be effectively used to remove different types of organic pollutants, such as cationic dyes (Amela et
329 al., 2012; Zhu et al., 2016), azo dyes (Tomczak and Tosik, 2017), direct dyes (Karthick et al., 2017), active
330 dyes (Hong and Wang, 2017; Tunç et al., 2009), vulcanization dyes and reduction dyes (Tran et al., 2017).
331 Furthermore, the functional groups of these agricultural wastes such as carbonyl (Bouguettoucha et al., 2016;
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332 Zhu et al., 2016), hydroxyl (Inam et al., 2015; Shang et al., 2015; Zhu et al., 2016), carboxyl (Bouguettoucha
333 et al., 2016; Inam et al., 2015), amine (Inam et al., 2015), amide (Sohrabi and Ameri, 2015), alcohols (Chebli
334 et al., 2015) and phenols (Bouguettoucha et al., 2016; Feng et al., 2015; Gülen et al., 2015) contribute to the
335 adsorption of dyes by various binding mechanisms (Lee et al., 2015). Thus, ion exchange (Charles et al.,
336 2016), complexation/coordination (Ji et al., 2007), adsorption (Sharma et al., 2016), electrostatic interaction
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337 (Safa, 2016), hydrogen bonding (Ahmad et al., 2014) and π-π stacking interaction (Wang et al., 2017)
338 adsorption mechanisms have been proposed. Safa (2016) found that mustard and linseed oil cakes can make
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339 use of electrostatic interaction to remove the acid dyes (Safa, 2016), and Marahel et al. (2013) also found this
340 mechanism when avocado integument removed basic red 2 (BR2) dye (Marahel et al., 2013).
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341 This section summarizes and comments on the application of agricultural wastes in the preparation of
342 adsorbents for adsorption of organic pollutants from five aspects of dyes, drugs, pesticides, aromatic
346 Growing demand for commercial dyes in various industries has led to the mass production of dyes. More
347 than 1.00×105 types of commercial dyes are available, with annual output exceeding 7.00×105 tons, most of
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348 them are directly discharged into the aqueous medium (Ansari et al., 2016). Water pollution can cause
349 numerous side effects such as mutagenicity, embryo toxicity, teratogenicity and carcinogenicity as well as
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350 damage to the liver, brain and central nervous and reproductive system resulting in abnormal renal function
351 (Tran et al., 2017). Dyes in natural water because of their content in aromatic hydrocarbons, metals, chlorides
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352 can lead to reduced transparency, damage to photosynthesis, damage to animals and plant growth, and affect
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353 the solubility of oxygen and self-cleaning process (Bouguettoucha et al., 2016; Tomczak and Tosik, 2017).
354 And because of its high water solubility, the dyes can be moved into the river affecting the water quality
356 In general, dyes are mainly anionic dyes (direct, acid and reactive dyes), cationic dyes (alkaline dyes) and
357 non-ionic dyes (disperse dyes) (Chebli et al., 2015; Zhou et al., 2015). At present, due to the harmfulness of
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358 dyes, many researchers are increasingly concerned about the removal of dyes, they choose to use simple and
359 easy agricultural waste (such as: rice husk, straw, coconut shell, olive powder) as adsorbent to study the
361
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362 4.1.1. Anionic dyes
363 Anion dyes is dependent on negative ions. They include many compounds from different types of dyes,
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364 structural differences (azo, anthraquinone, triphenyl methane and nitro dyes). For them, however, there is a
365 shared trait: water-soluble ionic substituents. Acidic dyes, direct dyes and reactive dyes are anionic dyes
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366 (Zhou et al., 2015).
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367 AN
368 4.1.1.1. Acid dyes
369 Acid dyes, acidic dyes have azo type, anthraquinone type, travel type, and most belong to azo dyes
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370 (https://baike.so.com/doc/5630201-5842822.html). Such as naphthol blue black (Palma et al., 2016), methyl
371 orange (Hosseinzadeh and Mohammadi, 2016; Mahmoud et al., 2017), acid blue 40 (Oei et al., 2009), amido
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372 black 10B (Ojha and Bulasara, 2015). The adsorption balance experiment was carried out by Safa (2015)
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373 through studying the dissolution of the new biomass oil mustard cake and flaxseed cake with Synolon black
374 HWF-FS and Synolon Red 3HF dye in batches. It found that the qm was 37.04 mg/g and 6.89 mg/g,
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375 respectively, and found its electrostatic interaction mechanism (Safa, 2015). Lee et al. (2017) found that the qm
376 of acid blue 113 dye adsorbed by Cucumis serious skin was 59.80 mg/g under the optimal conditions of pH
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377 6.0 and temperature 323K (Lee et al., 2017). The studies show that agricultural waste is a friendly and
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378 effective alternative to reduce the environmental pollution of acidic dyes. Although there are not a few studies
380
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382 The researchers explored the ability and mechanism of using agricultural waste as an adsorbent to eliminate
383 direct dyes through various experiments. Among them, Chebli et al. (2015) studied the use of a new low-cost
384 disorient Stipa tenassicima fibers that removed Congo red (CR) dye in aqueous solution, studied the
385 influencing factors and at pH 4.0, temperature 298K found that its qm was 7.93 mg/g. Its mechanisms of action
386 were: antiparticle diffusion, strong protonation and electrostatic interactions (Chebli et al., 2015). Shang et al.
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387 (2015) also tested for CR adsorption by using polyethyleneimine-modified straw to improve the adsorption
388 capacity. The results showed that at 303K, its qm was 89.70 mg/g through the Langmuir model. And it found
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389 that its mechanisms of action were mainly ion exchange and hydrogen bonding (Shang et al., 2015). In
390 addition, direct dyes include direct red 23 dyes (DR23). Fathi et al. (2015) evaluated the applicability and
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391 efficiency of corn stover (CS) removal of DR23 using isotherms, kinetics and thermodynamic models and
392 found it was very effective. And it is good to conclude that CS was a friendly adsorbent which removed DR23
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393 and it was easy to get (Fathi et al., 2015). According to different experimental studies, agricultural waste can
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394 be used for direct dyes adsorption effectively (Chebli et al., 2015). However, there is not much research on the
396
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398 Reactive dyes include reactive black 5 (RB5) (Palma et al., 2016), reactive blue 5G (RB5G) (Módenes et al.,
399 2015), reactive red 141 (Sreelatha et al., 2011), and reactive blue 21 (Sreelatha et al., 2011). Researchers
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400 studied the adsorption performance of different adsorbents on reactive dyes. For example, in the case of RB5
401 adsorption, Palma et al. (2016) explored the production of carbonaceous material in avocado skin by assessing
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402 the carbonization temperature and time effect, and by acid, alkali, reactive dye adsorption contrast, to explore
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403 the feasibility of carbonization materials (Palma et al., 2016). However, Oei et al. (2009) modified the barley
404 straw by nitrogen adsorption, titration and FTIR analysis, through the investigation of influencing factors
405 (adsorbent dosage, initial dye concentration, pH and temperature) to find the most suitable conditions (Oei et
406 al., 2009). Módenes et al. (2015) studied the removal of RB5G by drying biomass of low cost biosorbent
407 prepared from banana pseudostem (BPS). The results showed that the adsorption of RB5G dye was the
408 process of physical adsorption (Módenes et al., 2015). Reactive dyes are mainly used in dyeing and printing of
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409 cotton, hemp, viscose, silk, wool and other fibers and their blended fabrics, so for the removal of the research
410 is very important. Many studies have shown that agricultural waste, as a simple biological adsorbent, can
411 effectively remove reactive dyes, but more research is needed (Palma et al., 2016).
412
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413 4.1.2. Cationic dyes
414 Common cationic dyes include malachite green (MG) (Agarwal et al., 2016; Ren et al., 2016), BR2
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415 (Marahel et al., 2013), basic blue 41 (Palma et al., 2016), crystal violet (Smitha et al., 2012; Wang et al., 2017),
416 rhodamine B (Smitha et al., 2012; Wang et al., 2017), methylene green (Tran et al., 2017; Tran et al., 2017)
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417 and MB (Djelloul and Hamdaoui, 2015; Gülen et al., 2015; Zhu et al., 2016). Among them, MB is a cationic
418 dye that researchers are more concerned about, for example: using the rind as adsorbent to remove MB
419
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(Djelloul and Hamdaoui, 2015), sumac leaves as a low cost and effective biological adsorbent to remove MB
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420 (Gülen et al., 2015), using citric acid to repair the gas tea as MB adsorbent (Zhou et al., 2016). The
421 experiment using different agricultural wastes as adsorbents to adsorb MB concluded that the adsorption
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422 mechanism were mainly electrostatic interaction (Gülen et al., 2015; Nayak and Pal, 2017), particle internal
423 diffusion (Gülen et al., 2015; Nayak and Pal, 2017; Sharma et al., 2016; Zhu et al., 2016; Zhou et al., 2016),
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424 ion exchange (Nayak and Pal, 2017), boundary layer diffusion (Nayak and Pal, 2017; Sharma and Tiwari,
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425 2016; Zhu et al., 2016). In addition, Ren et al. (2016) used agricultural waste garlic as a adsorbent to remove
426 malachite green, through the Langmuir model, and found that at pH 8.0, temperature 298K, adding 2.00×103
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427 mg/L gallon particles, adsorption capacity was the largest 232.56 mg/g. And it was proved that garlic root can
428 be used as adsorbent which is low-cost, and can be used to remove dyes from industrial waste water (Ren et
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429 al., 2016). It is very necessary to reduce the pollution of the environment in the age when the dye is widely
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430 used. According to the recent research, agricultural waste as an environment-friendly adsorbent can effectively
431 adsorb cationic dye. However, there is no reason to stop exploring and further strengthen agricultural waste as
433
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435 Non-ionic dyes also refer to disperse dyes. At present, there are few studies on the removal of non-ionic
436 dyes from agricultural wastes as adsorbents. Bamboo stalk as precursor, pretreated activated carbon (AC) by
437 low-temperature chemical activation, and used AC to remove azo disperse red 167 (Zhou et al., 2015). Dyes
438 as a substance that is colored and harmful to human, other animals and plants, deserve greater attention from
439 researchers. More agricultural waste should be used to remove such substances as an adsorbent. The
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440 corresponding adsorption parameters of dyes are shown in the Table 8.
441
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442 4.2. Drugs
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443 Drugs are dangerous environmental contaminants around the world (Kyzas and Deliyanni, 2015). As a
444 newly recognized category of environmental pollutants, drugs have received considerable attention in terms of
445
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their environmental fate and toxicological nature (Kyzas and Deliyanni, 2015; Portinho et al., 2017). Drugs
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446 are made by humans and animals, unchanged or in metabolite form through urine and feces (Portinho et al.,
447 2017). Drugs bring convenience to humans, but they also cause pollution, and improper handling can lead to
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448 water, soil and other pollution. Therefore, the treatment of drugs is particularly important, especially
449 agricultural waste as adsorbent to remove drugs. The studies show that agricultural waste is an
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451
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453 Antibiotics can control infectious diseases and be used as feed additives to promote healthy growth (Wang
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454 et al., 2017). Since the introduction of penicillin into drug therapy in 1942, hundreds of other antibiotics have
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455 been isolated or synthesized for the treatment of human and animal infections (Qiao et al., 2018).With the
456 increasing use of antibiotics, environmental problems have gradually emerged. Researchers are also paying
457 more attention to the removal of antibiotics, which are the focus of researchers attention by using agricultural
458 waste as adsorbent to adsorb antibiotics. Yin et al. (2016) used iron ore to alter straw biomass (MSF) to
459 improve the ability of adsorbing the tylosin (TYL). The results showed that the main adsorption mechanism
460 was attributed to electrostatic interaction and hydrophobic interaction, in addition, it might be related to
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461 H-bonding and surface complexation. As a result, MSF was considered to be the removal of TYL scavengers
462 and had great potential for removing organic contaminants from aqueous solutions (Yin et al., 2016).
463 In antibiotics, tetracycline (TC) is a concern for researchers. TC is one of the most widely used antibiotics
464 and is often used in animal husbandry (Wang et al., 2017). Therefore, the removal of tetracycline is very
465 necessary. The study was designed to investigate the feasibility of removing TC from rice husk ash (RHA) as
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466 a new adsorbent, and the results showed that RHA was a cheap adsorbent for removing TC and reached the qm
467 8.37 mg/g at 313K (Chen et al., 2016). The experiment was a magnetic carbon composite with layered
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468 structure, which was used to prepare TC adsorption of bagasse by hydrothermal carbonation and simple heat
469 treatment process, the magnetic carbon composites exhibited qm 48.35 mg/g, and the chemical and mechanical
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470 properties were stable and the magnetic properties were good. The adsorption of TC by magnetic adsorbent
471 was mainly attributed to H-bonding and α-β interaction. The results showed that sugarcane bagasse in the
472
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sugar industry could be effectively converted into magnetic adsorbent to remove TC by environmental
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473 friendly methods (Rattanachueskul et al., 2016). The use of agricultural waste to absorb antibiotics will have a
474 great impact on human development. Therefore, researchers should devote more energy to the removal of
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475 antibiotics and other methods to explore. The use of antibiotics is one of the greatest advances in human
476 history, but at the same time it has brought harm to human beings and the environment. And if not
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477 governed,there will be unimaginable crises. At present, there are many experiments on the removal of
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478 antibiotics. Among them, agricultural waste as adsorbent has brought hope to researchers, which will have a
479 great impact on human development. Although there are many studies on the removal of antibiotics,
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480 researchers need to explore more accurate and effective ways to mitigate environmental pollution.
481
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483 In addition to antibiotics, there are anti-inflammatory drugs (diclofenac, ketoprofen, naproxen, nimesulide,
484 ibuprofen, diclofenac sodium) and other medications (Zhou et al., 2015). Portinho et al. (2017) investigated
485 the availability of caffeine from aqueous solution on grape stalk, observed better adsorption ability in acidic
486 solution, assessed balance by adsorption isotherm structure, and found the qm 916.70 mg/g (Portinho et al.,
487 2017). As one of the most dangerous contaminants, drugs need to be solved and removed. Experimental study
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488 using various agricultural wastes to remove drugs showed that agricultural waste is a good adsorbent and has
489 great potential. The corresponding adsorption parameters are shown in the Table 9.
490
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492 Pesticides can kill organisms that cause disease and can prevent, kill weeds, pests, fungi or microorganisms
493 (viruses and bacteria) (Trivedi et al., 2016). At present, the synthetic chemical pesticides are about 500 species.
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494 The widespread use of these pesticides, not only causes serious environmental pollution, but also hazards
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496 environment including air, soil and water (Peña et al., 2016). As an effective method of pesticide removal,
497 adsorption is favored by researchers, especially agricultural waste as adsorbent. For example, Gámiz et al.
498
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(2016) investigated how to repair agricultural soil with 2% of compost from olive mill waste or its biochar
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499 (BC), affecting the adsorption, degradation and leaching of two enantiomers of choral fungicide a cream. It
500 concluded that when BC was applied to soil, it can reduce pollution in agriculture and reduce the mobility of
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501 highly polar chiral pesticides (Gámiz et al., 2016). In addition, BC can be used as a fixed correction in soil
502 remediation and groundwater pollution prevention strategies. Peña et al. (2016) also conducted experiments
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503 on the adsorption of pesticides, which evaluated the effects of de-oiled two-phase olive mill waste on the
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504 behavior of metribuzin in the Mediterranean agricultural soil and assessed the effects of these wastes on the
506 2,4-dichlorophenoxyacetic acid (2,4-D) is a systematic, selective and popular herbicide and plant growth
507 regulator, and is widely used in broad-leaved plants worldwide. It is highly toxic and may be harmful to
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508 humans and animals (López-Cabeza et al., 2017). It was also reported by the International Agency for Cancer
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509 Research as carcinogenic and mutagenic agents (Trivedi et al., 2016). Therefore, the removal of 2,4-D has
510 become the focus of researchers. The H3PO4 -activated langsat empty fruit bunch was used by Njoku et al.
511 (2015) as a chelating agent for the production of AC to remove 2,4-D. It found the qm 332.00 mg/g and the
512 internal diffusion of particles was the main control mechanism (Njoku et al., 2015). Deokar et al. (2016) used
513 bagasse fly ash (BFA) as adsorbent to remove 2,4-D. The results showed that BFA can be an adsorbent which
515 Pesticides are characterized by high efficiency and high residual or low residue, among which many species
516 have high acute toxicity to mammals. So the hazards of pesticide use are not to be underestimated. Although
517 researchers have done a lot of research on the removal of pesticides, this is far from enough. In recent years,
518 the studies of agricultural waste as an adsorbent to remove pesticides have brought dawn to the researchers,
519 but further research is also needed to achieve more efficient and accurate. The corresponding adsorption
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520 parameters are in the Table 9.
521
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522 4.4. Aromatic compounds
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523 Organic Pollutants in addition to dyes, pesticides, pharmaceuticals and other organic compounds, there is a
524 class of the material-aromatic compounds that the researchers should pay attention to. Many aromatic
525
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compounds contain a benzene ring, which binds to one or more substituent groups (Ouellette and Rawn, 2015).
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526 Among them, polycyclic aromatic hydrocarbon is a kind of matter of concern. It is a toxic pollutant which is
527 produced in the process of fossil fuel combustion, which is a toxic, mutagenic, carcinogenic, almost
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528 biodegradable organic compound (Kronenberg et al., 2017; Lamichhane et al., 2017; Yang et al., 2017).
529 Aromatic compounds are classified by the United States Environmental Protection Agency and the European
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530 commission (Gupta and Gupta, 2015). They can be released in the water system through various sources, such
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531 as industrial waste water, agricultural runoff and polluted air deposition (Gupta and Gupta, 2015). And they
532 pose a great threat to the human body and the environment. Gupta and Gupta (2015) synthesized activated
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533 carbon from waste banana peel, aimed to remove polycyclic aromatic hydrocarbons from the water system,
534 established Langmuir and Freundlich model, and calculated characteristic parameters of adsorption isotherm.
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535 It concluded that the adsorbent prepared from banana peel can be easily used in industrial processing plants to
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536 remove polycyclic aromatic hydrocarbons (Gupta and Gupta, 2015). And the authors found that the removal
537 of sugar or hydrolytic biomass was a promising biological adsorbent for the removal of polycyclic aromatic
539 In addition, aromatic compounds include phenols and their derivatives (phenol, chlorophenol,
540 para-chlorophenol, ortho-Chlorophenol). Phenolic compounds have a water-soluble, highly toxic, adverse
541 impact on aquatic organisms and the environment (Karri et al., 2017). Phenolic compounds are highly mobile
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542 and soluble in water capacity, which can be mixed by natural drinking water downstream, causing serious
543 harm and health hazards to the human body (Karri et al., 2017). Therefore, the treatment of phenolic
544 compounds and their compounds is the key to ensure environmental and human health. At present, many
545 researchers have carried out studies on the removal of phenolic compounds from agricultural wastes as
546 adsorbents, and the main adsorption mechanisms are hydrogen bonding, hydrophobic interaction, π-π
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547 interaction, ion exchange, electronic sharing and exchange, electrostatic interaction, boundary layer diffusion,
548 particle internal diffusion (Feng et al., 2015; Shah et al., 2016; Tonucci et al., 2015; Tran et al., 2015). Feng et
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549 al. (2015) passed from cattails (Asha Orientalis Presl)preparation of activated carbon and evaluated the ability
550 of removing phenol, and the adsorption experiment found that the ionic strength of the effect of phenol
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551 removal was minimal, and concluded that Asha Orientalis Presl has great potential, and was an economic and
553
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Aromatic compounds, which are characterized by stable structure, easy decomposition and strong toxicity,
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554 cause serious pollution to the environment and cause great harm to human body. Therefore, the study of its
555 removal is particularly important. In recent years, researchers have done a lot of research, in which
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556 agricultural waste as adsorbent to remove aromatic compounds is a friendly and effective method.For its
557 removal, there have been great achievements.. But researchers cannot stop there and should continue to
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558 explore ways to be more efficient and green and apply them to industry. The corresponding adsorption
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560
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562 Oil pollution poses a serious threat to the environment. When oil floating into water, it can spread hundreds
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563 of miles, form thin layers and prevent oxygen moving from the atmosphere to aquatic organisms (Abdelwahab
564 et al., 2016). The largest source of pollution is oil substances (Zhou et al., 2015). In recent years, more and
565 more research has focused on agricultural waste as an adsorbent to remove oil, such as barley straw, coconut
566 shells, garlic and onion skins (Ibrahim et al., 2010; Zhou et al., 2015). Abdelwahab et al. (2016) modified the
567 bagasse by esterification and coating of polyacrylonitrile and used as a hydrophobic adsorbent to remove
568 diesel from man-made seawater. The adsorption mechanism is chemical adsorption, and it found that the
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569 maximum absorption of oil on all adsorbents can be arranged as follows: paraffin oil > vegetable oil > diesel
570 oil > petrol. The results showed that the prepared adsorbent can be actively involved in solving environmental
571 problems (Abdelwahab et al., 2016). In addition to petroleum products, emulsified oil is also a material
572 affecting the environment. Pachathu et al. (2015) studied the modified bagasse and straw as emulsified oil
573 absorption agent through the microwave-assisted technology. Under 313K, the maximum oil removal ratio of
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574 microwave-assisted bagasse and straw were 98.07% and 98.72%, respectively. It can be seen that the qm of
575 modified bagasse and rice straw were 192.58 mg/g and 276.82 mg/g, respectively (Pachathu et al., 2015). The
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576 research results showed that agricultural waste can be used as an effective adsorbent for oil products. In recent
577 years, the study on the adsorption of oil substances by agricultural waste as adsorbent was not much, so it
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578 should be further studied.
579
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580 4.6. Adsorption mechanisms for organic pollutant removal
581 The adsorption mechanism of organic pollutant removal depends on the nature of the pollutant and the
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582 chemical properties of the agricultural waste surface (Rosales et al. 2017). And it is also accompanied by a
583 variety of factors that affect each other. In the batch mode, the adsorption experiment of the
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584 polyethyleneimine-modified wheat straw (NWS) on CR was carried out by Shang et al. (2015). The
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585 experiment has shown that in NWS there were varieties of floristic fibers and some functional groups
586 including carboxyl, hydroxy and amides, which can be used for adsorption process. H-bonding was the
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587 principal adsorption mechanism of the adsorption process, and it also accompanied with a variety of
588 mechanisms (Shang et al., 2015). Wang et al. (2017) studied the adsorption of tetracycline by activated carbon
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589 prepared by straw at different temperatures and found that the π–π electron-donor acceptor and the high
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590 surface area of the biochar samples derived from rice straw that were pyrolyzed at 973K made its high
591 adsorption capacity (Wang et al., 2017). Scholar studied the magnetic composite materials prepared by
592 bagasse to remove tetracycline, and found that the oxygen-containing functional groups on the surface of the
593 adsorbent played a dominant role in the adsorption of TC. The oxygen-containing groups on the complex
594 adsorbent and the -OH, C=O and -NH2 on the TC molecule form H bonds. In addition, the surface of the
595 composite has a partially aromatic characteristics, indicating that an electron donor-acceptor (EDA)
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596 interaction, or cation-bonding, can form a cationic bond with the conjugate in the TC molecule ring. The
597 specific mechanism of the adsorbent and TC is shown in Fig. 6 (Rattanachueskul et al., 2016). Shah et al.
598 (2016) studied the adsorption of chlorine-chlorophenol on zeolite composites derived from bagasse fly ash.
599 The experimental results shown that the adsorption process were dominated by π-π interaction and affinity
600 formation of donor acceptor complexes on the adsorbent surface (Shah et al., 2016). Electrostatic effect is also
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601 the main mechanism of agricultural waste adsorption organic pollutants. Many researchers had come to the
602 same conclusion by experiments (Fathi et al., 2015; Krishna et al., 2017; Mashhadi et al., 2016). In addition,
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603 Deokar et al. (2016) used bagasse fly ash as an adsorbent to remove 2,4-dichlorophenoxyacetic acid. The
604 result shown that the molecules form of 2,4-D mainly due to Van Der Waals interaction was adsorbed on the
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605 surface of BFA, while the anionic form may be due to electrostatic interaction was adsorbed (Deokar et al.,
606 2016). Fan et al. (2016) used the activated carbon derived from hazelnut shell to remove tetracycline
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607 antibiotics, indicating that electron donor–acceptor, hydrogen bonding, and π-π dispersion interaction between
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608 the aromatic ring of three antibiotics are the main adsorption mechanisms. And the kinetic analysis shown that
609 the adsorption process can ascribe to external transfer and intraparticle diffusion (Fan et al., 2016). On the
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610 other hand, the adsorption mechanism of MB onto adsorbent including physical adsorption and chemical
611 adsorption was studied (Fan et al., 2016). Due to the different chemical composition of various agricultural
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612 wastes, the surface active groups and functional groups are different, which results in different mechanisms of
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613 the adsorption organics by various agricultural wastes (see Fig. 7). In this paper, the qm and mechanisms of
615
617 With the increasingly serious environmental problems, in addition to inorganic and organic pollutants,
618 harmful gases have become the focus of global attention. At present, global warming and climate change are
619 already a major threat to human survival, and human beings are facing melting glaciers, rising sea levels and
620 other problems. The rapid increase of greenhouse gases is one of the reasons. Two main types of greenhouse
621 gases include carbon dioxide (CO2) and nitrous oxide (N2O). In 2017, the concentration of CO2 in the
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623 Excessive CO2 stimulates the human respiratory center, causing shortness of breath and headaches,
624 confusion and other symptoms. N2O greenhouse effect was about 300 times serious than CO2 (Yan et al.,
625 2016). Dizziness, loss of direction and balance, memory loss, cognitive impairment, and weakness in the legs
626 are all the side effects of N2O. Severe or prolonged use of N2O can cause vitamin B12 inactivation, leading to
627 functional vitamin B12 deficiency, initial finger numbness, and possibly further development of peripheral
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628 neuropathy and giant cell anemia (Amsterdam and Nabben, 2015). Currently, research on greenhouse gases
629 mainly focuses on the capture and storage of gas. In recent researches, adsorption has the characteristics of
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630 high efficiency and low pollution, so it is a suitable technology for this pollution. Moreover, biochar is a cheap
631 and easily available adsorbent. Nowadays, many agricultural wastes are used for adsorb harmful gases.
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632 Through the activation of CO2, ammonification with ammonia (NH3) and the treatment of soybean straw with
633 CO2 and NH3 at high temperature, Zhang et al. (2016) found that the optimum activation conditions were
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634 obtained and the qm was 49.87 mg/g (Zhang et al., 2016). Erto et al. (2016) pointed out that the removal of
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635 CO2 by pyrolysis and steam-activated agricultural waste mainly relied on the high micropore volume and
636 narrow pore size distribution (Erto et al., 2016). Shahkarami et al. (2015) identified the main differences of the
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637 surface chemistry, porous structure and morphology of activated carbon obtained through rapid and slow
638 pyrolysis of agricultural waste, and obtained the qm 78.10 mg/g (Shahkarami et al., 2015). A research about
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639 the adsorption of 16 volatile organic compounds in the gas phase by activated carbon from waste rice hulls,
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640 and proposed the adsorption mechanism were hydrogen bonding and non-specific interaction (Li et al., 2016).
641 Scholar also made use of rice husk as adsorbent, and developed an effective adsorbent of flue gas removal by
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642 modification (Zhu et al., 2016). These studies show that agricultural waste can play a significant role in the
643 removal of greenhouse gases, and its adsorption mechanism mainly depends on the high micropore volume,
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644 narrow pore size distribution, hydrogen bonding and non-specific interaction. Harmful gases in a certain
645 extent will endanger the survival of mankind. The problem of accumulation for agricultural wastes is also
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646 urgent to be solved. The use of waste as an adsorbent to remove greenhouse gases can solve both problems.
647 However, there are still few researches in this area, which still need to be further explored by researchers.
648
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651 The use of agricultural waste as adsorbent for fixed bed adsorbers removes organic substances in water, and
652 is often used in drinking water treatment, groundwater remediation, and swimming pool water treatment
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653 (Shao, 2013). The current adsorber for treating the water phase is designed as a closed pressure filter or an
654 open gravity filter. The material of the filter is usually corrosion-resistant steel or concrete. The adsorbent in a
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655 fixed bed adsorber is located at the bottom of the perforation, and water typically flows down through the
656 adsorbent bed. Between the activated carbon and the bottom there is a small layer of sand used to remove the
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657 toner(see Fig. 8). As the most common adsorbent for water treatment, agricultural waste exists in two forms:
658 powdered and granular. Granular agricultural waste is used in fixed bed adsorbers.
659
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In a wastewater treatment plant, multiple adsorbers in series can make the fixed bed adsorption process a
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660 continuous process, reducing capacity loss. In principle, there are two ways to connect a single fixed bed
661 adsorber to a multiple adsorber system: series and parallel. The total sorbent mass was divided into four
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662 adsorbers, only three adsorbers were running, and the other was stopped to regenerate the adsorbent. The time
663 t1 indicates the time point at which the adsorber 1 is inactive and the mass transfer zone (MTZ) is located
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664 between the adsorbers 3 and 4 . As the MTZ has left the adsorber 2, the adsorbent in the adsorber is fully
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665 saturated to equilibrium. Therefore, the adsorber 2 will be the next stop. The time t2 indicates a later time. So
666 on and so forth. In an ideal situation, all adsorbers can be operated until the entire adsorbent bed reaches the
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667 equilibrium load. The total flow to be treated is divided into a plurality of substreams which are supplied to a
668 plurality of adsorbers operating in parallel. Different adsorbers are put into use at different starting times.
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669 Therefore, at a given time, the travel distance of MTZ in different adsorbers is different, so the breakthrough
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670 time is also different. Different concentrations of different sorbent effluents are mixed to obtain a total effluent
671 stream. The main advantage of parallel connections is that the total cross-sectional area increases with the
672 number of adsorbers. Therefore, this multi-adsorber system is very flexible and can be adjusted according to
673 the different requirements of the amount of water that needs to be treated. It is particularly suitable for
675
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677 The use of bio-carbon derived from agricultural waste such as sugarcane bagasse (Youssef, 1981) as Carbon
678 Molecular Sieve (CMS) to isolate gas is another important application of agricultural waste in industry.
679 Researcher found three fluxes in the hole through the "selective surface Flow" carbon film: flux, Knudsen flux,
680 and diffusion through the surface (Rao and Sircar, 1993a). Surface diffusion can be the main flux of pore
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681 diffusion when the surface concentration is high or when other fluxes are low (Kapoor et al., 1989). Moreover,
682 when the pore size is about twice times that of the strongly adsorbed molecule, the adsorbed molecule
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683 effectively reduces the pore openings, thereby eliminating or hindering the fluxes of other adsorbed or weakly
684 adsorbed molecules, and eventually enhancing the separation. The successful application of the separation
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685 principle depends on the fabrication of a membrane with controllable and uniform aperture, through the poly
686 (two) vinyl chloride controlled pyrolysis experiment supported on the macroporous alumina tube(Golden et al.,
687
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1998). The principle of CMS membrane is shown in Fig. 9 (Golden et al., 1998).
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688 CMS membrane has a relatively unique distribution of molecular size of the membrane hole, good
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689 separation and mechanical properties as well as high stability. Therefore, the CMS membrane can be used in
690 air O2/N2 separation, H2 recovery, CO2 enrichment, low carbon hydrocarbon separation and He recovery, and
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692
694 The study of adsorbent regeneration can effectively prevent secondary pollution caused by waste adsorbents
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695 (Anirudhan and Sreekumari, 2011). At present, commonly used adsorbent regeneration methods include
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696 solvent extraction, calcination, and biological methods. The solvent extraction method uses an appropriate
697 solvent to extract the adsorbate from the adsorbent. The calcination method is to adsorb the adsorbed
698 adsorbent at a high temperature to convert the adsorbate into a gas or a volatile substance, thereby recovering
699 the adsorbent's adsorption capacity. Emerging bioremediation utilizes microorganisms to desorb the adsorbent
700 and achieve desorption and regeneration of the adsorbent, which is characterized by simple operation, low
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702 In the experiment, hydrochloric acid, sulfuric acid, and nitric acid are commonly used to desorb the heavy
703 metal ions adsorbed by the biomass adsorbent by placing an adsorbent that has adsorbed heavy metal ions in
704 an acidic solution and competitively adsorbing the heavy metal ions by H+ ions to make the heavy metal ions.
705 Replace it for regeneration. The experiment was carried out by using 0.1 mol/L hydrochloric acid to
706 desorption of algae Oedogonium sp. which adsorbed Cd2+. The adsorption capacity of algae in 4 cycles was
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707 42.8 mg/g, 40.1 mg/g, 38.8 mg/g, 36.5 mg/g and 34.2 mg/g, respectively (Gupta and Rastogi, 2008). Another
708 study was carried out used a 0.1 mol/L hydrochloric acid solution as a desorption agent. The desorption humic
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709 acid adsorbent was activated with 0.1 mol/L NaOH solution, and then the adsorbent was washed with
710 ultrapure water. The next cycle of adsorption experiments was performed with propargite adsorbents.
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711 Repeatedly for 5 cycles, the adsorption of Cd2+ were 20.12 mg/g, 19.35 mg/g, 18.96 mg/g, 18.52 mg/g, and
712 18.13 mg/g, respectively (Chen et al., 2014). It can be seen that the biomass adsorbent can be used repeatedly
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713 and has good practical application value.
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714
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716 At present, China is the country with the largest output of agricultural waste all over the world. When its
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717 agricultural waste in the process of not being effective use, to a certain extent, increased the burden of rural
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718 agricultural production, more importantly, also caused the pollution of the rural environment. Therefore,
719 increasing the reuse of agricultural wastes can effectively reduce the air pollution caused by plant incineration.
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720 The soil pollution caused by the residues of heavy metals and pesticides in plants, fixed N/P to replenish soil
721 nutrients and improve soil quality of cultivated land. Meanwhile, it also can prevent the water pollution
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722 caused by livestock manure and the spread of bacteria and viruses caused by the long-term decay of
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723 agricultural wastes, and improve the ecological environment (Liu, 2017).
724 From domestic and international studies, it can be seen that agricultural waste is an ideal choice to deal with
725 pollutants and improve its adsorption effect by modifying their properties. However, researchers often ignore
726 the size of environmental pollution caused by the modification process, the complexity of the modified
727 process and the level of the modified cost. Biochar is an idiographic renewable resource and has great
728 potential to solve several environmental problems in recent years, including remediation of contaminants in
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729 soil, water and gaseous media (Rosales et al., 2017). The utilization of agricultural wastes for bio-carbon is the
730 core international competitive technology of green low-carbon agriculture, which is the current international
731 agricultural soil carbon sequestration, waste environmental management, resource recycling and energy
732 saving and emission reduction, and tackling climate change. This technology is to research and develop
733 various types of carbonization technology of agricultural waste biomass and promote the industrialization of
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734 biochar, which can effectively alleviate a series of realistic ecological and environmental problems, such as
735 the increase of carbon emissions caused by the rapid economic development, the increase of environmental
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736 pollution and the increase of greenhouse gas emissions.
737 This paper argues that the future directions of agricultural waste as adsorbent are:
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738 (1) Research and develop of agricultural waste biomass carbonization technology to promote the
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739 industrialization of biomass carbon.
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740 (2) Development of high efficiency green modifier and modification process will be the development
742 (3) Future research should also extend to the use of agricultural waste adsorbents to deal with the
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744 In summary, biomass adsorbents based on agricultural waste show significant advantages and can be used
745 to replace expensive commercial activated carbon for environmental pollution control. This provides a broad
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747
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748 9. Conclusions
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749 With the development of economy, regional environmental pollution and large-scale ecological destruction
750 have become increasingly serious, threatening the survival and development of all mankind. Wide range of
751 sources, low-cost, renewable biosorbents is becoming more and more popular. Agricultural wastes with loose
752 and porous structure contain carboxyl, hydroxyl and other active groups, which can remove pollutants better.
753 Its adsorption is effected by the pH, temperature, initial concentration and other factors. Modified agricultural
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754 waste can get a better adsorption effect. Its main mechanisms of adsorbing pollutants are ion exchange,
755 electrostatic interaction, complex adsorption and others are still under further exploration. This paper believes
756 that the development of efficient green modifier and technology will be the development direction of
757 biological adsorption. Using agricultural waste as biomass adsorbent can not only reduce the environmental
758 burden but also achieve the goal of "treating waste by waste". In the future environmental governance, it will
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759 have broad space for development.
760
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761 Acknowledgement
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762 This work was supported by Program of Student Innovation Practice Training (SIPT) of Northeast
764
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765 References
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1008 Mor, S., Chhoden, K., Khaiwal, R., 2016. Application of agro-waste rice husk ash for the removal of
TE
1010 Moyo, M., Chirinda, A., Nharingo, T., 2016. Removal of copper from aueous solution using chemically
EP
1011 treated potato (solanum tuberosum) leaf powder. Clean-Soil Air Water 44(5), 488-495.
C
1012 Najam, R., Andrabi, S.M.A., 2016. Removal of Cu(II), Zn(II) and Cd(II) ions from aqueous solutions by
1013 adsorption on walnut shell-Equilibrium and thermodynamic studies: treatment of effluents from
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1015 Naushad, M., Khan, M.A., Alothman, Z.A., Khan, M.R., Kumar, M., 2015. Adsorption of methylene blue on
1016 chemically modified pine nut shells in single and binary systems: isotherms, kinetics, and thermodynamic
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1018 Nayak. A.K., Pal, A., 2017. Green and efficient biosorptive removal of methylene blue by Abelmoschus
1019 esculentus seed: Process optimization and multi-variate modeling. J. Environ. Manage. 200, 145-159.
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1021 phosphate from aqueous solutions and sewage using Zirconium Loaded Okara (ZLO): Fixed-bed column
PT
1023 Nguyen, T.A.H., Ngo, H.H., Guo, W.S., Zhang, J., Liang, S., Yue, Q.Y., Li, Q., Nguyen, T.V., 2013.
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1024 Applicability of agricultural waste and by-products for adsorptive removal of heavy metals from
SC
1026 Njoku, V.O., Islam, M.A., Asif, M., Hameed, B.H., 2015. Adsorption of 2,4-dichlorophenoxyacetic acid by
1027 mesoporous activated carbon prepared from H3PO4-activated langsat empty fruit bunch. J. Environ.
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1029 Oei, B.C., Ibrahim, S., Wang, S.B., Ang H.M., 2009. Surfactant modified barley straw for removal of acid and
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M
1031 Ojha, A. K and Bulasara V.K., 2015. Adsorption characteristics of jackfruit leaf powder for the removal of
D
1032 amido black 10B dye. Environ Prog Sustain. 34(2). 461-470.
TE
1033 Omidvar-Hosseini, F., Moeinpour, F., 2016. Removal of Pb(II) from aqueous solutions using acacia nilotica
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1035 Ouellette, R.J., Rawn, J.D., 2015. Aromatic compounds. Principles of Organic Chemtry. 133-162.
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1036 Palma, C., Lloret, L., Puen, A., Tobar, M., Contreras, E., 2016. Production of carbonaceous material from
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1042 pH, ionic strength, and humic acid on cadmium adsorption onto activated biochar: Experiment and
1044 Peña, D., López-Piñeiro, A., Albarrán Á., Rato-Nunes, J.M., Sánchez-Llerena, J., Becerra, D., Ramírez, M.,
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1047 Pirbazari, A.E., Saberikhah, E., Gorabi N.G.A., 2014. Fe3O4 nanoparticles loaded onto wheat straw: an
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1048 efficient adsorbent for Basic Blue 9 adsorption from aqueous solution. Desalin. Water Treat. 57(9),
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1050 Portinho, R., Zanella, O., Féris L.A., 2017. Grape stalk application for caffeine removal through adsorption. J.
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Prasanthi, M.R., Jayasravanthi M., Nadh R.V., 2016. Kinetic, thermodynamic and equilibrium studies on
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1055 Qian, L., Chen, B., 2013. Dual role of biochars as adsorbents for aluminum: the effects of oxygen-containing
D
1056 organic components and the scattering of silicate particles. Environ. Sci. Technol. 47 (15), 8759-8768.
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1057 Qian, L., Zhang, W., Yan, J., Han, L., Gao, W., Liu, R., Chen, M., 2016. Effective removal of heavy metal by
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1059 Qiao, M., Ying, G.G., Singer, A.C., Zhu, Y.G., 2018. Review of antibiotic resistance in China and its
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1083 low-cost biosorbent: From batch assays to continuous-flow systems. Bioresour. Technol. 246, 176-192.
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1108 Shao, Y., 2013. Adsorption dynamics of phenolic wastewater in structures fixed bed. Ph. D. Dissertation,
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1114 Singha, A. S., Guleria A., 2014. Utility of chemically modified agricultural waste okra biomass for removal of
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1129 Tang, R.X., Dai, C., Li, C., Liu W.H., Gao S.T., Wang, C., 2017. Removal of methylene blue from aqueous
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1130 solution using agricultural residue walnut shell: equilibrium, kinetic, and thermodynamic studies. J. Chem.
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1133 removal and adsorption mechanisms of cadmium and lead from aqueous solution by activated carbons
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1138 Tonucci, M.C., Gurgel L.V.A., Aquino, S.F.D., 2015, Activated carbons from agricultural byproducts (pine
1139 tree and coconut shell), coal, and carbon nanotubes as adsorbents for removal of sulfamethoxazole from
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1156 Wang, H., Chu Y.X., Fang C.R., 2017. Sorption of tetracycline on biochar derived from rice straw under
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1158 Wang, L.H., 2012. Application of activated carbon derived from ‘waste’ bamboo culms for the adsorption of
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1161 method for xylitol bioconversion with high-temperature steaming corncob hydrolysate by adapted candida
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1163 Wang, P., Ma, Q,Y., Hu, D.Y., Wang, L.J., 2015. Adsorption of methylene blue by a low-cost biosorbent: citric
1164 acid modified peanut shell. Desalin. Water Treat. 57(22), 10261-10269.
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1187 bioethanol production by rice straw. Energy 135, 32–39.Zhou, R.S., Zhou, R.W., Zhang X.H., Tu, S., Yin
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CO2 adsorption: effects of temperature. RSC Adv. 100, 98157-98166.
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1197 Zhou, Y., Zhang, L., Cheng, Z.J., 2015. Removal of organic pollutants from aqueous solution using
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1200 capture of SO2/NO by ammonium halides modified rice husk char. Fuel 172, 160-169.
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1206 Zhu, Y.Y., Kolar, P., Shah, S.B., Cheng, J.J., Lim, P.K., 2016. Avocado seed-derived activated carbon for
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Grain crop straw
production
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Forest residues, Vegetable melons
17.33% vines and residue
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42.47% production
Oil crop straw yield
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Crop straw,
56.82%
4.74% Cotton stalk yield
Livestock and
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poultry manure,
25.85% 4.53% Others
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3.28%
1.80%
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100
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Chemical composition (%)
Others
75
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Lignin
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50
Hemicellulos
e
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Cellulose
25
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0
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CEP
AC
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(Chan et al., 2015; Chen et al., 2016; Chen et al., 2017; Heng et al., 2017; Hesami et al., 2015;
Katsimpouras et al., 2016; Robl et al., 2016; Rohowsky et al., 2013; Wang et al., 2011; Zhang et al., 2017)
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Fig. 5. The possible mechanism of heavy metal ion adsorption (Singha and Guleria, 2014)
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Fig. 6. The adsorption mechanism of TC on a magnetic composite derived from sugarcane bagasse
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(Rattanachueskul et al., 2016)
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Fig. 8. Typical fixed-bed adsorbers in water treatment: (a) pressure GAC filter made
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(Worch, 2012)
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Table 1 Maximum adsorption capacity and mechanism of Pb (II) on different agricultural wastes
SC
Pollutant Agricultural waste pH Temperature(K) qm (mg/g) Sorption mechanism Reference
U
Andes Salsa Inch shell biomass 3.0 323 17.07 Electrostatic attraction Kumar et al., 2016
AN
6.0 298 18.98 Monolayer chemisorption Guo et al., 2015
Acid-modified rice straw
M
and ion exchanges
D
Coconut shell 26.14
TE
5.5 298 Chemisorption El-Deen et al., 2016
Pb (II) Activated coconut shell 49.92
EP
Rice straw 5.5 298 42.55 Electrostatic attraction and
Amer et al., 2017
physical adsorption
C
Moeinpour., 2016
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Alkali-treated persimmon fallen 5.0 303 256.00 Electrostatic attraction, ion
Fan et al., 2016
leaves exchange and chelation
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AN
M
D
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Table 2 Maximum adsorption capacity and mechanism of Cd (II) on different agricultural wastes
C
Cd (II) Phragmites australis 6.0 _ 5.41 Film diffusion Farasati et al., 2015
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6.0 313 7.29 Share or exchange electronics Najam et al., 2016
Raw walnut shell
and chemisorption
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Alkali treated walnut shell 6.0 303 14.29 Ion exchange Gondhalekar et al., 2015
SC
Salix matsudana carbon 5.0 298 40.98
Chemisorption and
Tang et al., 2017
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intra-particle
Typha angustifolia carbon 5.0 298 48.08
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Sesame 6.0 298 84.74 Chemisorption Cheraghi et al., 2015
M
Succinate-bonded pullulan 7.0 298 476.20 Ion exchange Abbas et al., 2015
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Table 3 Maximum adsorption capacity and mechanism of Cu (II) on different agricultural wastes
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Sorption
Pollutant Agricultural waste pH Temperature(K) qm (mg/g) Reference
mechanism
M
Casuarinas fruit powder 4.55
D
Chemisorption and
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Banana stem powder 5.0 303 6.49 Mokkapati et al., 2016
physical adsorption
Sorghum stem powder 7.97
EP
Cu (II)
Watermelon shells 8.0 298 9.54 _ Mohammed et al., 2016
C
Andes Salsa Inch shell 6.0 323 9.70 Electrostatic Kumar et al., 2016
AC
biomass
attraction
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Raw pomegranate peel 5.8 323 21.37
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powder
SC
Chemically Treated Potato 6.5 298 42.74 _ Moyo et al., 2016
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Plum stone 5.5 298 48.31 _ Parlayıcı et al., 2017
AN
Potato peel 5.0 298 84.74 Particle diffusion Guechi et al., 2015
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Table 4 Maximum adsorption capacity and mechanism of Ni (II), Zn (II) and Mg (II) on different agricultural wastes
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Litrus limetta Peel
27.07
(Nonlinear)
Singh and Shukla,
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6.0 _ Ion exchange
2017
Litrus limetta Peel
27.78
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(Linear)
U
Chelation Chand et al., 2014
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Chemically modified 6.0 256.40
apple pomace
M
Tabacco stem 5.3 298 97.32 _ Rao et al., 2014
Ni (II)
D
Cocoa shell-prepared at 97.59
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ambient temperature
6.0 303 Intra-particle diffusion Kalaivani et al., 2014
Cocoa shell-prepared at 158.80
EP
623K
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Hemp fiber 6.0 293 206.00 Intra-particle diffusion Kyzas et al., 2015
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5.0 313 7.48 Ion exchange Najam and Andrabi,
Walnut shell
2016
Zn (II)
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Fennel seeds 6.5 293 _ _ Laskar et al., 2016
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Mg (II) Raw date pits 5.0 293 38.50 Ion exchange Rezgui et al., 2016
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AN
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Table 5 Maximum adsorption capacity and mechanism of Cr (VI) on different agricultural wastes
Cr (VI) Rice husk 6.0 298 18.20 Metal reduction and ion exchange Ding et al., 2016
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Raw Sterculia guttata shell 2.0 333 45.45 Electrostatic attraction Prasanthi et al., 2016
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Polypyrrole modified natural
3.5 298 84.70 Ion exchange Zhang et al., 2016
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corncob-core sponge
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Table 6 Maximum adsorption capacity and mechanism of Hg (II), As (III) and As (V) on different agricultural wastes
SC
Pollutants Agricultural waste pH Temperature(K) qm (mg/g) Sorption mechanism Reference
U
Peanut shell 6.0 308 6.60 Surface complexation Bai et al., 2015
AN
Raw date pits 5.0 293 52.63 Ion exchange Rezgui et al., 2017
M
Unmodified rice husk 75.19
D
Hg (II) Unmodified rice straw 91.74
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6.5 303 Ion exchange Song et al., 2015
Sulfur-fuctionalized rice husk 98.33
EP
Sulfur-fuctionalized rice straw 125.00
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Table 7 Maximum adsorption capacity and mechanism of NH4+, NO3- and PO43- by different agricultural wastes in varying pH and temperature
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Rice husk (adsorption from pure NH4Cl) 303 71.94
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Wood (adsorption from slurry solutions) 318 78.06
9.8
SC
Wood (adsorption from pure NH4Cl) 303 133.33
U
7 298 Ion exchange Mao et al., 2015
AN
PSBMIHM-AE 100.2
M
6.5 297 Kalaruban et al., 2016
NO3- Amine-grafted coconut copra 59.20 _
D
Quaternary Starch 6.5 303 205.00 Ion exchange Chauhan et al., 2016
Corncob TE
5.65 297 0.04 Ion exchange
Micháleková-Richveisová
EP
et al., 2017
PO43-
Activated Rice Husk Ash 6 303 0.74 Physical adsorption Mor et al., 2016
C
AC
PT
RI
SC
Table 8 Maximum adsorption capacity and mechanism of dyes on different agricultural wastes
U
Agricultural waste Dyes pH Temperature (K) qm(mg/g) Sorption mechanism Reference
AN
Camelina-derived Methylene blue 6.0 323 5.08
Intraparticle diffusion, Surface adsorption Sharma and Tiwari, 2016
M
Sapindus-derived Methylene blue 6.0 323 50.76
D
Chemisorption, Physisorption, Electrostatic Gülen et al., 2016
Sumac leaves Methylene blue 5.0 298 5.80
TE
Interactions
Synolon black
EP
Linseed oil cake 2.0 6.89
HWF-FS
_ Electrostatic Interactions Safa, 2016
C
Stipa tenassicima fibers Congo red 4.0 298 7.93 Strong protonation, Electrostatic Interactions Chebli et al., 2015
Earthworm manure Rhodamine B 2.0 600 21.60 Ion exchange, Hydrogen bonding, Electrostatic Wang et al., 2017
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PT
Malachite green 27.00
Stem of Solanum tuberosum
RI
Methylene blue 41.60
7.0 303 Physisorption Gupta et al., 2016
Malachite green 33.30
SC
Leaves of Solanum tuberosum
Methylene blue 52.60
U
Sesame waste Reactive red 141 1.1 293 27.55 Electrostatic Interactions Sohrabi and Ameri, 2015
AN
Bengal gram fruit shell (BGFS) Acid blue 25 2.0 308 29.41 Electrostatic Interactions, Intraparticle diffusion Krishna et al., 2017
M
Coconut coir dust Cationic dye 6.0 303 29.50 Interaction, Electrostatic force Etim et al., 2016
D
Crystal violet 33.22
TE
Cucumis sativus 7.0 300
Rhodamine B 35.33
EP
Boundary layer diffusion, Intraparticle diffusion Smitha et al., 2012
Crystal violet 40.82
Sulfuric acid-Cucumis sativus 6.3 300
C
Rhodamine B 34.01
AC
Table 8 Continued
Banana pseudostem Reactive blue 5G 1.0 303 37.01 Ion exchange, Physisorption Módenes et al., 2015
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Corn stalks Direct Red 23 3.0 318 51.87 Electrostatic Interactions Fathi et al., 2015
PT
Water Bamboo Leaves Methylene blue 6.8 283 54.17 Intraparticle diffusion , Electrostatic Interactions Zhu et al., 2016
Walnut Shell Methylene blue 6.0 318 56.13 Chemical reaction Tang et al., 2017
RI
Cucumis sativus peel Acid Blue 113 6.0 323 59.81 Chemisorption Lee et al., 2015
SC
Rice straw-Microwave induced
Methylene blue 7.0 298 62.50 H-bonding, Electrostatic attraction Mashhadi et al., 2016
U
-H2SO4 activation
AN
Ion exchange, Chemical reaction, Electrostatic
Avocado integument BR2 dye 7.0 303 102.45 Marahel et al., 2013
Interactions, Protonation of surface groups
M
Potato (Solanum tuberosum)
D
Methylene blue 6.2 298 105.26 Physisorption, Electrostatic Interactions Guechi et al., 2015
peel
Polyethyleneimine-
Congo red 5.0 TE
313 118.00
H-bonding, Van Der Waals, π-π conjugate, Ion
Shang et al., 2015
EP
modified wheat straw exchange
Citric acid modified peanut shell Methylene blue 303 120.48 Electrostatic attraction Wang et al., 2015
C
AC
Abelmoschus esculentus seed Methylene blue 6.7 600 168.63 Ion exchange, Chemisorption Nayak and Pal, 2017
Chemically modified pine nut Methylene blue 5.9 328 182.08 Dipole-dipole interaction, π-π interaction Naushad et al., 2015
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shells
PT
Ion exchange, Chemical reaction, Electrostatic
Alfa grass Methylene blue 12.0 293 200.00 Toumi et al., 2015
Interactions, External diffusion
RI
Aminated pumpkin seed Methylorange 3.0 318 200.30 Electrostatic Interactions Subbaiah and Kim, 2016
SC
Durian Seed - KOH Synthetic Dye 2.0 303 357.14 H-bonding Ahmad et al., 2014
U
Complexes adsorption, Ion exchange,
Fe3O4-wheat straw Basic Blue 9 7.0 323 627.10 Pirbazari et al., 2014
AN
Deprotonation
Table 9 Maximum adsorption capacity and mechanism of other organic pollutants on different agricultural wastes
M
Agricultural wastes Organic contaminants pH Temperature(K) qm(mg/g) Sorption mechanism Reference
D
TE
2,4-dichlorophenoxyacetic
Bagasse fly ash 3.5 328 7.14 Van Der Waals Deokar et al., 2016
acid
EP
Electrostatic Interactions, The sharing or
Typha orientalis Presl Phenol 5.0 313 7.23 Feng et al., 2015
C
exchange of electrons
AC
Modified sugarcane
Tetracycline 6.8 303 48.35 H-bonding, π-π interaction Rattanachueskul et al., 2016
bagasse
PT
Rice husk 63.50
RI
Fluoroquinolone 5.1 309 H-bonding Ashrafi et al., 2015
NaOH-modified rice husk 241.00
SC
Tetracycline (TC) 312.50
Hazelnut shell derived H-bonding, π-π electron donor-acceptor,
U
Oxytetracycline (OTC) 5.0 293 322.60 Fan et al., 2016
activated carbons p–p dispersion interaction
AN
Chlortetracycline (CTC) 333.30
M
D
TE
C EP
AC
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HIGHLIGHTS
agricultural wastes.
PT
Future prospects of agricultural wastes as adsorbents were discussed.
RI
U SC
AN
M
D
TE
C EP
AC