Chemosphere 211 (2018) 235e253

Contents lists available at ScienceDirect

Chemosphere
journal homepage: www.elsevier.com/locate/chemosphere

Review

Utilizations of agricultural waste as adsorbent for the removal of

contaminants: A review
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*
Laboratory of Environmental Remediation, College of Resources and Environment, Northeast Agricultural University, No.600 Changjiang Road, Xiangfang
District, Harbin 150030, China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Summarized the research progress of

adsorbing inorganics, organics and
gases on agricultural wastes.

Expounded the mechanism of
adsorption inorganics and organics
by agricultural wastes.

The application of agricultural waste
as adsorbents in engineering was
introduced.

Future prospects of agricultural
wastes as adsorbents were discussed.

a r t i c l e i n f o a b s t r a c t

Article history: In recent years, various industrial activities have caused serious pollution to the environment. Due to the
Received 5 May 2018 low operating costs and high flexibility, adsorption is considered as one of the most effective technol-
Received in revised form ogies for pollutant management. Agricultural waste has loose and porous structures, and contains
28 June 2018
functional groups such as the carboxyl group and hydroxyl group, so it can be invoked as biological
Accepted 29 June 2018
adsorption material. Agricultural waste gets the advantages of a wide range of sources, low cost, and
Available online 17 July 2018
renewable. It has a good prospect for the comprehensive utilization of resources when used for envi-
Handling Editor: Dr Y Yeomin Yoon ronmental pollution control. This article summarized the current research status of agricultural waste in
adsorbing pollutants, which pointed out the influencing factors of adsorption, expounded the adsorption
Keywords: mechanism of biological adsorption and introduced the related parameters of adsorption, proposed the
Agricultural waste application of adsorbents in engineering including adsorption in liquid and gas phases, at the same time
Contaminant it gave the future development prospect of agricultural waste as adsorbent.
Removal © 2018 Published by Elsevier Ltd.
Adsorption

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
2. Types, structures and resource utilization of agricultural waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.1. Types and structures of agricultural wastes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

* Corresponding author.
E-mail address: zhangyinghr@hotmail.com (Y. Zhang).

https://doi.org/10.1016/j.chemosphere.2018.06.179
0045-6535/© 2018 Published by Elsevier Ltd.
236 Y. Dai et al. / Chemosphere 211 (2018) 235e253

2.2. The resource utilization of agricultural waste . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238

3. Remove inorganic contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.1. Heavy metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
3.1.1. Lead . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1.2. Cadmium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1.3. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1.4. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3.1.5. Other heavy metal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
3.2. Nitrogen and phosphorus . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241
4. Remove organic contaminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
4.1. Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4.1.1. Anionic dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4.1.2. Cationic dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
4.1.3. Non-ionic dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.2. Drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.2.1. Antibiotics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.2.2. Other drugs . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.3. Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
4.4. Aromatic compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.5. Oil substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
4.6. Adsorption mechanisms for organic pollutant removal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 246
5. Get rid of the gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
6. Application of adsorbents in engineering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
6.1. Adsorption in liquid phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
6.2. Adsorption in the gas phase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 248
7. Adsorbent regeneration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
8. Future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 249
9. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250

1. Introduction output of waste is estimated to exceed 5.00  109 tons in China

(Tao, 2013).
Agricultural waste is a general term for organic substances With the rapid development of industry and the over-
discarded by human beings in the process of agricultural produc- exploitation of natural resources, environmental pollution has
tion. It mainly includes plant waste, livestock and poultry manure, caused serious harm to human health, so it is urgent to solve
agricultural and sideline products processing waste, rural house- ecological problems. Conventional methods for removing con-
hold waste. Agricultural waste, which originates from our life, taminants from gaseous and aqueous phases are mainly biological
mainly refers to crop stalks and animal manure (Liu, 2017). It is treatment, flocculation (Jawad et al., 2015), membrane separation
characterized by a wide range of sources, large quantity, repro- processes, chemical precipitation, adsorption (utilizing activated
ducible, biodegradable and environmental-friendly. Research carbon) and ion exchange (Rosales et al., 2017). Among these
showed that the total agricultural wastes in 2013 was 1.75  109 methods, adsorption has been shown to be an effective and cost-
tons in China, of which crop straw was 9.93  108 tons, accounting effective method for removing many pollutants (Ashrafi et al.,
for 56.82%, livestock and poultry manure was 4.52  108 tons, ac- 2015a,b). In adsorbents, activated carbon adsorption is an effec-
counting for 25.85%, forest residues were 3.03  108 tons, ac- tive and reliable method. Activated carbon has the benefits of high
counting for 17.33% (Zuo, 2015). Fig. 1 shows the proportion of surface area, micro-porous structure, uniform pore size distribu-
agricultural wastes. In addition, with the rapid development of tion, high porosity, high surface reactivity, superior mechanical
social economy and the increase of population, total waste pro- strength and strong adsorption capacity (Mashhadi et al., 2016a,b).
duction will increase at a rate of 5%e10% a year and the annual However, the high cost of this approach has prompted the search

Fig. 1. The agricultural wastes' output of China in 2013.

 Y. Dai et al. / Chemosphere 211 (2018) 235e253
for alternative industries (Jawad et al., 2015). Agricultural waste has
a loose, porous structure and contains carboxyl, hydroxyl and other
reactive groups, can be used as a biomass adsorption material in the
field of pollution control, which can not only reduce the environ-
mental burden but also achieve the effect of “treating waste by
waste” (Huang, 2017). The agricultural wastes used for distortion
mainly include straw (Salem and Yakoot, 2016), wheat straw
(Shang et al., 2015a,b), bagasse (Rattanachueskul et al., 2016), ba-
nana skin (Gupta and Gupta, 2015), walnut shell (Tonucci et al.,
2015), coconut shell (Tang et al., 2017a,b), avocado skin (Marahel
et al., 2013; Palma et al., 2016), olive powder (Ga
miz et al., 2016;

pez-Cabeza et al., 2017; Pen
Lo ~ a et al., 2016), mustard (Safa, 2016;
Trivedi et al., 2016), linen (Safa, 2016; Sharma et al., 2016), cu-
cumber (Lee et al., 2015; Smitha et al., 2012), waste tea (Zhou et al.,
2015), earthworm feces (Wang et al., 2017a,b).
At present, a great deal of researches has been made at home
and abroad on taking advantage of agricultural wastes as biomass
adsorbents for the treatment of pollutants. Numerous researchers
have done a lot of research on the use of agricultural waste to
adsorb heavy metals. Salmania et al. (2017) studied the removal of
cadmium ions by magnetized biochar based on orange peel and
conventional orange peel (Salmania et al., 2017). Houda and
Moussa (2017) studied that using banana waste to remove zinc
ions from aqueous solutions. In addition, many researchers studied
to remove extra dense metal (Houda and Moussa, 2017). In organic
adsorption, Djelloul and Hamdaoui (2015) researched the kinetic
adsorption of methylene blue (MB) by melon peel in packed col-
umns (Djelloul and Hamdaoui, 2015). Shang et al. (2015a,b) studied
the use of thermally activated pinecone as a low cost adsorbent to
remove dimethyl trisulfide from aqueous solutions (Shang et al.,
2015a,b). Currently adsorption has been successfully employed to
remove inorganic, organic pollutants and gases in the environment.
However, research on gas is comparatively fewer.
In recent years, a great deal of agricultural waste has been
generated every year around the world. At present, extensive
agricultural waste disposal methods not only fail to effectively
Fig. 2. Agricultural waste as adsorbent application.
237
convert and utilize agricultural resources, but also cause serious
environmental pollution. A large amount of N2O, SO2, CH4 and
smoke are generated during the process of fecal burning and rice
straw incineration, which seriously pollutes the atmosphere (Wei,
2013). In addition to organic matter in livestock and poultry
manure, there are mass pathogenic bacteria, parasitic eggs and
heavy metal. They are given directly into the water without proper
treatment, causing serious contamination of groundwater and
surface water systems (Wei, 2013). Traditional organic fertilizers
have been gradually superseded by chemical fertilizers and other
chemical materials, due to the widespread use of pesticides. Fer-
tilizers greatly narrows the quality of the soil and the soil buffer
capacity. Therefore, improving the reuse of agricultural wastes
could effectively replenish soil nutrients enhances the quality of
arable land (Liu, 2017). In the face of agricultural waste and
ecological environmental damage caused by agricultural waste,
researching on the utilization of agricultural waste has caused
widespread concern. The rationalization of agricultural wastes is of
profound significance to effectively alleviate the environmental
pollution and improve the ecological environment.
In order to comprehend the research progress of agricultural
wastes as adsorbents, this paper reviews the literature in recent
years. At present, Zhou et al. (2015) reviewed the removal of
organic pollutants on agricultural wastes. Nguyen et al. (2013)
summarized the removal of heavy metals from water using agri-
cultural waste. Rosales et al. (2017) reviewed the development of
biochar as a low cost adsorbent. However, there was not any
comprehensive review on the application (remove organic, inor-
ganic and gas) of agricultural waste as adsorbent. The main purpose
of this paper was to present a summary of the latest information on
the use of agricultural waste as an adsorbent in environmental
management (see Fig. 2). The article (i) introduced the mechanism
of removing inorganic (heavy metals, N and P), organic matter
(dyes, drugs, pesticides, aromatic compounds, and oil substances)
and gases respectively; (ii) listed the adsorption parameters of
typical agricultural wastes under the experimental conditions; (iii)
238 Y. Dai et al. / Chemosphere 211 (2018) 235e253
analyzed the factors affecting the adsorption process; (iv) made a
forecast on the future development of agricultural waste.
2. Types, structures and resource utilization of agricultural
waste
2.1. Types and structures of agricultural wastes
Agricultural wastes are lignocellulosic materials and the main
structural components are lignin, cellulose and hemicellulose
(Salleh et al., 2011). Lignin is only an aromatic polymer, which
consists of carbonyl, hydroxyl, methyl and other functional groups.
Both hemicellulose and cellulose contain oxygen functional groups
including carbonyl groups, hydroxyl groups and ether. These
functional groups can bind heavy metal ions and organic small
molecule contaminants by cheating, completing, coordinating,
hydrogen bonding and the like, which play an important part in the
preparation of adsorbents (Zhou et al., 2015). Chemical composition
analysis of conventional agricultural wastes is presented in Fig. 3.
When agricultural waste absorbed heavy metal ions, the dynamic
functional groups took an important role, in which O element can
form coordination bonds with heavy metals (Wen et al., 2017). The
focal mechanism, by which agricultural wastes adsorb dyes was
generally influenced by several processes (Shah et al., 2016). In
general, agricultural waste directly acts as an adsorbent and re-
searchers are now paying much attention to increase the adsorp-
tion capacity of cultivated waste through modification (chemical
and physical). Ashrafi et al. (2015a,b) optimized adsorption condi-
tions for basic blue 41 based on the Box-Behnken design response
surface methodology using NaOH-modified rice husk. It is shown
that the method of NaOH modification can be used to improve the
rice husk to raise the adsorption capacity (Ashrafi et al., 2015a,b).
Abdelwahab et al. (2016) separated the oil from water through
polymer coated partially esterified sugarcane bagasse (Abdelwahab
et al., 2016). In general, modification can improve the adsorption
capacity of agricultural wastes.
2.2. The resource utilization of agricultural waste
Agricultural waste is highly available and is utilized in a variety
of ways. At present, there are mostly five aspects of resource
100
Chemical composition (%)
75
50
25
Fig. 3. Chemical composition of some typical agriculture waste (% dry weight).
(Chan et al., 2015; 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).
utilization of agricultural waste. Fertilizer utilization, making the
waste into fertilizer and soil conditioner by using agricultural waste
fertilizer technology, which can lead to the return of organic fer-
tilizer to the soil, increase the organic content of the soil, ensure the
organic minerals need for the growth of the plant, improve the soil
structure and reduce the application of chemical fertilizers and
pesticides (Deng, 2017). Feed utilization, using the crop straws as
feed, which will help animal digestion and absorption. It can largely
curb the burning of straw and reduce greenhouse gas emissions.
The industrialization and construction raw materials of agricultural
waste mean that is used as a raw material for paper making and the
output of polymer panels instead of wood. Energy utilization of
agricultural wastes mainly includes anaerobic fermentation and
direct pyrolysis. Converting agricultural waste into electricity is
direct combustion pyrolysis. It largely contained open-air straw
burning and coal combustion. So it can hold back the occurrence of
acid rain, to a certain extent. Optimization is utilizing the proper
treatment of agricultural waste as a substrate material for mush-
rooms, vegetables production (Chen and Shi, 2017). In addition,
agricultural waste is a natural, environmental and economic
adsorbent source. Because of its loose surface, porous, superior
mechanical strength and chemical stability, it is appropriate for the
restoration of ecological pollution. However, there is poorly
researched on agricultural wastes as adsorbents at present, so it is
of great significance to consider the application of agricultural
wastes as adsorbents.
3. Remove inorganic contaminants
3.1. Heavy metal
The rapid advance of industrialization and rapid urbanization
has resulted in the excessive discharge of heavy metal-containing
wastewater into the environment, seriously affecting human
health (Zhang et al., 2016a). These metallic elements have been
defined as mutagenic and carcinogenic agents, and may be toxic to
aquatic life (EPA, 2017). Over decades, numerous cadmium reme-
diation techniques, broadly classified into chemical precipitation,
flotation, ion exchange, adsorption and membrane filtration, have
been established for cadmium removal. These methods have sig-
nificant disadvantages, including elevated energy requirements,
Others
Lignin
Hemicellulos
e
Cellulose
 Y. Dai et al. / Chemosphere 211 (2018) 235e253
incomplete metal removal, generation of toxic sludge, demanding
treatment and expensive equipment (Farhan et al., 2012). In this
context, proscription has proved to be a promising method, with
such benefits as: (1) the minimization of chemical sludge; (2) low
cost of promotion and without detrimental effects on the envi-
ronment (Du et al., 2016). Fig. 4 accurately describes the mecha-
nisms of adsorption of heavy metal ions in agricultural wastes
including chemical adsorption, physical adsorption, ion exchange,
membrane diffusion, particle diffusion, chelation, electrostatic
attraction, surface complexation, ligand exchange and internal
complexation. An increasing number of studies have shown that
agricultural waste can contribute to immobilization of heavy
metals (Qian and Chen, 2013; Qian et al., 2016). This section will
describe in the adsorption of several archetypal heavy metal ions by
agricultural waste.
3.1.1. Lead
Lead is detrimental heavy metal to the body. Lead and its
compounds enter the body that will do harm to the nervous, car-
diovascular, hematopoietic, kidney, digestive and endocrine and
other systems. If the content is overproof, it will cause lead
poisoning. With the rapid progress of the industrial market, lead
has been widely used in all walks of life. Simultaneously, it causes
environmental pollution and health hazards to the human body. At
present, lead affects human health mainly through food, drinking
water, air and other approaches (http://baike.asianmetal.cn/metal/
pb/health.shtml). The maximum allowable concentration of lead in
drinking water is 15.00  103 mg/L (EPA, 2017). Amer et al. (2017)
has been established that rice husk was an efficient adsorbent for
adsorbing Pb (II) in experiments (Amer et al., 2017). The disruption
was due to multiple mechanisms: Surface complexation with car-
boxylic and hydroxyl functional groups, ion exchange with Ca (II),
Mg (II), and physical forces of attraction. They found the benefits of
rice husk as an adsorbent. Pb (II) can be marked by using an acid
and eventually recovered. Rice straw can be regenerated for a
Fig. 4. The adsorption mechanism of inorganic pollutants on agricultural waste.
239
certain number of cycles. So the resources can be stored. El-Deen
and El-Deen (2016) did some experiments and found the phos-
phoric acid activated coconut shell (ACS) adsorbed more Pb (II) than
inactivated coconut shell (CS) (El-Deen and El-Deen, 2016). They
operated a series of adsorption experiments to measure the use of
the ACS as a dissolution agent for the absorption of lead in waste-
water and to compare it with pyrolysis of CS. The results demon-
strate that the biological adsorbent (ACS) is under a high surface
area and functional groups. Table 1 shows the adsorption of lead by
other agricultural wastes. As can be seen from the figure, there are
many kinds of agricultural wastes that can absorb lead ions, which
is a method worthy of being promoted to handle heavy metal ion
pollution.
3.1.2. Cadmium
Cadmium (Cd) is seen as an extremely toxic metal without a
known biological function (Wang et al., 2010). Cadmium accumu-
lates in the human body, especially in the kidneys and it can lead to
insufficiency of renal function. Being dependent on the World
Health Organization and its recommended standard values, the
permissible limit of cadmium in drinking water was 0.005 mg/L.
Cadmium is widely used in various kinds of industrial activities
(e.g., pigment manufacture, refining of non-ferrous metals), and the
subsequent release of cadmium-containing wastewater into the
environment has become a focus of global concern over the past
years, due to its high toxicity, environmental accumulation and
non-biodegradable characteristic (Park et al., 2017). Gondhalekar
and Shukla (2015) studied the principal mechanism for Cd (II)
removal utilizing raw walnut shell was ion exchange (Gondhalekar
and Shukla, 2015). Because the ester and acetyl operative groups
have been changed to carboxylate, the ability of dissolution
increased. Singha and Guleria (2014) used succinylated cellulosic
biomass as adsorbent to remove heavy metal ions (Singha and
Guleria, 2014). Studies have found that ion exchange is the main
mechanism. The possible mechanism is shown in Fig. 5. Two
adjacent carboxyl and hydroxyl groups are attached by a divalent
heavy metal ion, and two pairs of electrons can be given to the
metal ion to form four coordination number compounds and
release the two sodium ions and protons into the solution. Farasati
et al. (2015) compared the adsorption ability of Phragmites australis
(P. australis) with sugarcane stalks on cadmium ions (Farasati et al.,
2015). They discovered the reason why sugarcane stalks adsorbed
more Cd (II) than P. australis were the most extended surface area
and softer surface. Chen et al. (2015) evaluated biochar derived
from geophysical dried sewage sludge through pyrolysis at 1173 K
(Chen et al., 2015). The results showed a minimal contribution of
organic matters on cadmium removal whereas alkaline earth
metals such as calcium was in charge of the adsorption process
owing to cation exchange and surface precipitation by the forma-
tion of insoluble cadmium salt under alkaline conditions. In addi-
tion, there is ample data in Table 2 indicating that agricultural
waste can absorb cadmium as an adsorbent. Consequently, agri-
cultural waste will be a popular cheap adsorption in the future
according to its non-pollution exchange progress and high removal
rate. At present, there is less research on cadmium ion adsorption in
agricultural waste, and more research is needed.
3.1.3. Copper
Copper and its alloys (brass and bronze) have been used in or-
dinary household wiring, photovoltaic cells and phytotherapy
products as fungicides, fertilizers, algicides and insecticides. The
EPA has set the acceptable limit of copper in drinking water at
1.30 mg/L. Table 3 shows manifold groups of cultivated waste
adsorbed copper ion data. Removal of Cu (II) from aqueous solution
via adsorption has been extensively employed in the wastewater
240 Y. Dai et al. / Chemosphere 211 (2018) 235e253

Table 1
Maximum adsorption capacity and mechanism of Pb (II) on different agricultural wastes.

Pollutant Agricultural waste pH Temperature(K) qm (mg/ Sorption mechanism Reference

g)

Pb (II) Andes Salsa Inch shell biomass 3.0 323 17.07 Electrostatic attraction Kumar et al., 2016
Acid-modified rice straw 6.0 298 18.98 Monolayer chemisorption and ion exchanges Guo et al., 2015
Coconut shell 5.5 298 26.14 Chemisorption El-Deen and El-Deen, 2016
Activated coconut shell 49.92
Rice straw 5.5 298 42.55 Electrostatic attraction and physical adsorption Amer et al., 2017
Plantain peels 6.0 50.51 _ Omidvar-Hosseini and Moeinpour.,
2016
Plum stone 5.5 298 80.65 _ Parlayıcı and Pehlivan, 2017
Hazelnut husk 5.0 298 109.90 _ Imamoglu et al., 2016
Alkali-treated persimmon fallen 5.0 303 256.00 Electrostatic attraction, ion exchange and Fan et al., 2016a,b
leaves chelation

Fig. 5. The possible mechanism of heavy metal ion adsorption (Singha and Guleria, 2014).

Table 2
Maximum adsorption capacity and mechanism of Cd (II) on different agricultural wastes.

Pollutant Agricultural waste pH Temperature (K) qm (mg/g) Sorption mechanism Reference

Cd (II) Phragmites australis 6.0 _ 5.41 Film diffusion Farasati et al., 2015
Sugarcane straw 4.0 _ 8.00
Raw walnut shell 6.0 313 7.29 Share or exchange electronics and chemisorption Najam and Andrabi, 2016
Alkali treated walnut shell 6.0 303 14.29 Ion exchange Gondhalekar and Shukla, 2015
Salix matsudana carbon 5.0 298 40.98 Chemisorption and intra-particle Tang et al., 2017a,b
Typha angustifolia carbon 5.0 298 48.08
Sesame 6.0 298 84.74 Chemisorption Cheraghi et al., 2015
Succinate-bonded pullulan 7.0 298 476.20 Ion exchange Abbas et al., 2015

Table 3
Maximum adsorption capacity and mechanism of Cu (II) on different agricultural wastes.

Pollutant Agricultural waste pH Temperature(K) qm (mg/g) Sorption mechanism Reference

Cu (II) Casuarinas fruit powder 5.0 303 4.55 Chemisorption and physical adsorption Mokkapati et al., 2016
Banana stem powder 6.49
Sorghum stem powder 7.97
Watermelon shells 8.0 298 9.54 _ Mohammed and Ibrahim, 2016
Andes Salsa Inch shell biomass 6.0 323 9.70 Electrostatic attraction Kumar et al., 2016
Walnut shell 5.0 313 14.54 _ Najam and Andrabi, 2016
Raw pomegranate peel 5.8 323 21.37 Ion exchange Ali et al., 2017
Platanus orientalis leaf powder 6.0 333 49.94
Chemically Treated Potato 6.5 298 42.74 _ Moyo et al., 2016
Plum stone 5.5 298 48.31 _ Parlayıcı and Pehlivan, 2017
Potato peel 5.0 298 84.74 Particle diffusion Guechi and Hamdaoui, 2015a,b

treatment plant (Jin et al., 2016). When a large amount of dense these two organs appeared problems, the body's metabolism would
metal remains in the human body, it is not hard to make the body's be frightened. Guechi and Hamdaoui (2015a,b) studied the
organs heavy burden especially the liver and gall bladder. When adsorption of copper ions by potato peel (PP) (Guechi and
 Y. Dai et al. / Chemosphere 211 (2018) 235e253
Hamdaoui, 2015a,b). They found that the adsorption kinetics ab-
sorption of Cu (II) at different initial metal ions was analyzed by
pseudo level, pseudo two levels and particle internal diffusion
model. It was pointed out that the maximum adsorption capacity
(qm) was 84.74 mg/g at 298 K. The thermodynamic parameters of
Cu (II) adsorption on PP were also calculated. The results showed
that PP was a type of adsorbent suitable for removing Cu (II) from
aqueous solution. Mokkapati et al. (2016) also studied difference
among three kinds of agricultural waste (banana stem powder,
casuarinas fruit powder, sorghum stem powder) (Mokkapati et al.,
2016). They did a lot of experiments to study the impact of different
factors on the adsorption effect. The qm for the three adsorbents for
Cu (II) was 6.50 mg/g, 4.50 mg/g and 7.90 mg/g, respectively. The
mechanism of banana stem powder and casuarinas fruit powder is
chemisorptions, and the mechanism of sorghum stem powder is
the combination of both physisorption and chemical attachment.
So they affirmed the three adsorbents could remove Cu (II) from
aqueous environment.
3.1.4. Nickel
Nickel is the human body essential life element, and in the
human body content is extremely tiny. Under normal circum-
stances, the human body contains the nickel to 10.00 mg and the
blood normal concentration is 0.11 mg/L. Nickel is also the most
widespread sensitization of metal. Nickel ions can penetrate
through the pores and sebaceous glands inside the skin, leading to
allergic inflammation of the skin. Once into sensitization symp-
toms, nickel allergy can be indefinitely sustained. More worrying
thing is the poisoning resulted from excessive intake of nickel. The
mortal body is daily intake of soluble nickel 250.00 mg will cause
poisoning. And the peculiar symptoms are dermatitis, respiratory
disorders and respiratory tract cancer (http://baike.asianmetal.cn/
metal/ni/health.shtml). Many experiments in Table 4 showed that
nickel ions could be absorbed by a variety of agricultural wastes.
Singh and Shukla (2017) proved that the waste citrus limits peel
was a cheap and abundantly available biomass, which showed
excellent potential for adsorbing Ni (II) (Singh and Shukla, 2017).
Ion exchange mechanism was involved in dissolution which re-
ceives the support of FTIR, isotherm and desorption studies. Under
the most suitable physical and chemical conditions, qm was
27.78 mg/g. Desorption studies using HCl showed almost complete
recovery of Ni (II) ions. Hence, citrus limits peels owing to its porous
structure, high sorption rate, low cost, and comparatively high
uptake capacity for Ni (II) ions, is a promising bioscience for com-
mercial applications.
Table 4
Maximum adsorption capacity and mechanism of Ni (II), Zn (II) and Mg (II) on different agricultural wastes.
Pollutants Agricultural waste pH Temperature(K)
Ni (II) Litrus limetta Peel (Nonlinear) 6.0 _ 27.07
Litrus limetta Peel (Linear)
Apple pomace 5.0 303
Chemically modified apple pomace 6.0
Tabacco stem 5.3 298
Cocoa shell-prepared at ambient temperature 6.0 303
Cocoa shell-prepared at 623 K
Hemp shive 6.0 293
Hemp fiber
Treated hemp shive
Treated hemp fiber
Zn (II) Walnut shell 5.0 313
Fennel seeds 6.5 293
Mg (II) Raw date pits 5.0 293
241
3.1.5. Other heavy metal
In addition to the above mentioned abundant heavy metal ions,
there are many other heavy metal ions that can also have an in-
fluence on human health, for example, Mercury has chronic toxicity
to human. Song et al. (2015) found rice husk and rice straw could
absorb Hg (II) by ion exchange (Song et al., 2015). Chromium can
cause dermatitis, eczema, bronchitis and rhinitis, causing allergic
reactions and carcinogenic effects. Ding et al. (2016) conducted a
series of experiments and found that the rice husk had the qm of
rice husk for Cr (VI) adsorption was 18.20 mg/g at pH 6.0 and room
temperature. Too much zinc can cause poisoning, for example,
excessive intake of zinc can cause acute zinc poisoning, vomiting,
diarrhea and other gastrointestinal symptoms, chronic zinc
poisoning may have anemia and other symptoms (Ding et al., 2016).
Najam and Andrabi (2016) using experimental data showed that
the walnut shell adsorbed Zn (II) through the mechanism of ion
exchange (Najam and Andrabi, 2016). Tables 5 and 6 shows in the
adsorption of metal ions by multiple sets of data. However, there
becomes less research on these kinds of heavy metal ions in agri-
cultural wastes, and the research on these metals can be deepened
in the future.
3.2. Nitrogen and phosphorus
Agricultural waste cannot be only adsorb heavy metal, but also
þ
adsorb nitrogen and phosphorus (NO3, PO3 4 , NH4 -N). This section
summarizes the data on the adsorption of Nitrogen and phos-
phorus from agricultural wastes through the literature search in
Table 7. Generally, the surfaces of most carbon-rich and low-
mineral biochars are negatively charged and have little or no abil-
ity to delete anions, particularly PO3 4 (Jung et al., 2015; Yao et al.,
2011). For example, Kizito et al. (2015) has studied wood and rice
husk adsorption of ammonium ions in NH4Cl solution and slurry
solutions (Kizito et al., 2015). It was noted that the adsorption effect
was accomplished in the case of chemisorption and physisorption,
and qm reached 133.33 mg/g, 78.06 mg/g, 71.94 mg/g and 59.56 mg/
g, respectively. In addition, Zhu et al. (2016a,b,c,d) studied the av-
ocado seed at 298 K, pH of 5.0 by an ion exchange mechanism
reached the gm of 5.40 mg/g (Zhu et al., 2016a,b,c,d). Jung et al.
(2015) discovered that biochars derived from soybean stover,
bamboo wood, and maize residue showed no sorption capacity for
PO3 3
4 removal and even released inherent PO4 into the solution
(Jung et al., 2015). Nguyen et al. (2015) modified to study the
adsorption of zirconium loaded Okara to PO3 4 , and the experi-
mental results showed that at room temperature, when zirconium
loaded okara in acidic environment with pH of 3.0, its qm was
16.43 mg/g (Nguyen et al., 2015). In short, agricultural waste can
qm (mg/g) Sorption mechanism Reference
Ion exchange Singh and Shukla, 2017
27.78
83.33 Chelation Chan et al., 2015
256.40
97.32 _ Rao et al., 2014
97.59 Intra-particle diffusion Kalaivani et al., 2014
158.80
160.00 Intra-particle diffusion Kyzas et al., 2015
206.00
237.00
242.00
7.48 Ion exchange Najam and Andrabi, 2016
_ _ Laskar et al., 2016
38.50 Ion exchange Rezgui et al., 2017
242 Y. Dai et al. / Chemosphere 211 (2018) 235e253

Table 5
Maximum adsorption capacity and mechanism of Cr (VI) on different agricultural wastes.

Pollutant Agricultural waste pH Temperature (K) qm (mg/g) Sorption mechanism Reference

Cr (VI) Teff straw 2.0 298 3.51 Chemisorption Tadesse et al., 2014
Rice husk 6.0 298 18.20 Metal reduction and ion exchange Ding et al., 2016
Raw Sterculia guttata shell 2.0 333 45.45 Electrostatic attraction Prasanthi et al., 2016
ZnCl2 activated Sterculia guttata shell waste 90.90
Polypyrrole modified natural corncob-core sponge 3.5 298 84.70 Ion exchange Zhang et al., 2016a,b,c

Table 6
Maximum adsorption capacity and mechanism of Hg (II), As (III) and As (V) on different agricultural wastes.

Pollutants Agricultural waste pH Temperature(K) qm (mg/g) Sorption mechanism Reference

Hg (II) Peanut shell 6.0 308 6.60 Surface complexation Bai et al., 2015
Raw date pits 5.0 293 52.63 Ion exchange Rezgui et al., 2017
Unmodified rice husk 6.5 303 75.19 Ion exchange Song et al., 2015
Unmodified rice straw 91.74
Sulfur-fuctionalized rice husk 98.33
Sulfur-fuctionalized rice straw 125.00
Rice straw 5.0 313 500.00 _ Mashhadi et al., 2016a,b
As (III) Bi impregnation-wheat straw 4.0 298 43.15 Ligand exchange Zhu et al., 2016a,b,c,d
As (V) Magnetic gelatin-modified chestnut shell 9.3 318 0.27 Electrostatic attraction and innersphere complexation

Table 7
Maximum adsorption capacity and mechanism of NHþ  3
4 , NO3 and PO4 by different agricultural wastes in varying pH and temperature.

Pollutant Agricultural waste pH Temperature(K) qm(mg/g) Sorption mechanism Reference

NHþ
4 Avocado seed-derived 5 298 5.40 Ion exchange Zhu et al., 2016a,b,c,d
Rice husk (adsorption from slurry solutions) 7.8 318 59.56 Chemisorption and physical adsorption Kizito et al., 2015
Rice husk (adsorption from pure NH4Cl) 303 71.94
Wood (adsorption from slurry solutions) 9.8 318 78.06
Wood (adsorption from pure NH4Cl) 303 133.33
SB-AE (Sugarcane bagasse) 7 298 73.40 Ion exchange Mao et al., 2015
PSBMIHM-AE 100.2
NO
3 Amine-grafted corn cob 6.5 297 49.90 _ Kalaruban et al., 2016
Amine-grafted coconut copra 59.20 _
Quaternary Starch 6.5 303 205.00 Ion exchange Chauhan et al., 2016
PO3-
4 Corncob 5.65 297 0.04 Ion exchange Mich

alekov
a-Richveisov

a et al., 2017
Activated Rice Husk Ash 6 303 0.74 Physical adsorption Mor et al., 2016
Zirconium loaded okara 3 298 16.43 _ Nguyen et al., 2015

absorb N and P, through chemisorption and physisorption, ion ex-
change mechanism, and the enriched bio-carbon obtained after
adsorption can be used as slow-release fertilizer for horticulture
and agriculture (Nguyen et al., 2015).
4. Remove organic contaminants
In recent years, with the continuous use of emerging organic
products, it has caused pollution problems such as water and soil.
At present, the application of agricultural waste as adsorbent in
water and soil to remove all kinds of organic pollutants has been a
great effort. Among them, the studies of pollutants are mainly dyes
(methylene blue (MB), rhodamine B, crystal violet, malachite green,
Congo red) (Chebli et al., 2015; Feng et al., 2015; Nayak and Pal,
2017; Ren et al., 2016; Smitha et al., 2012; Wang et al., 2017a,b),
drugs (tetracycline, caffeine, tylosin) (Portinho et al., 2017; Yin
et al., 2016), pesticides (metalaxyl, metribuzin,
dichlorophenoxyacetic acid) (Ga
miz et al., 2016; Pen
~ a et al., 2016;
Trivedi et al., 2016), aromatic compounds (polycyclic aromatic hy-
drocarbons, phenol) (Gupta and Gupta, 2015; Karri et al., 2017) and
oil substances (emulsified oil, diesel oil, lubricating oil)
(Abdelwahab et al., 2016; Chai et al., 2015).
A number of treatment techniques have been developed to
remove organics, such as flocculation (Guan and Tian, 2017), sedi-
mentation (Wen et al., 2017), light treatment (Deng et al., 2017),
membrane processes (Sarasidis et al., 2017), chemical oxidant
oxidation (Gayathri et al., 2017), biological oxidation (Chen et al.,
2017), photo-catalytic oxidation/degradation (Janssens et al.,
2017), adsorption (Huang et al., 2017) and combined methods
(Sandoval et al., 2017; Zhou et al., 2015). Among them, adsorption is
the most concerned because of its high removal rate and simple
operation. However, conventional adsorbents such as activated
carbon are cost-effective, and it is not economically viable to ach-
ieve their widespread use in the removal of organic contaminants.
Therefore, the bio-adsorbent prepared by theunassuming, easy and
low-cost agricultural waste has become the focus of the re-
searchers. At present, various biosorbents prepared from agricul-
tural waste can be effectively used to remove different types of
organic pollutants, such as cationic dyes (Amela et al., 2012; Zhu
et al., 2016a,b,c,d), azo dyes (Tomczak and Tosik, 2017), direct
dyes (Karthick et al., 2017), active dyes (Hong and Wang, 2017; Tunç
et al., 2009), vulcanization dyes and reduction dyes (Tran et al.,
2,4- 2017a,b). Furthermore, the functional groups of these agricultural
wastes such as carbonyl (Bouguettoucha et al., 2016; Zhu et al.,
2016a,b,c,d), hydroxyl (Inam et al., 2015; Shang et al., 2015a,b;
Zhu et al., 2016a,b,c,d), carboxyl (Bouguettoucha et al., 2016; Inam
et al., 2015), amine (Inam et al., 2015), amide (Sohrabi and Ameri,
2015), alcohols (Chebli et al., 2015) and phenols (Bouguettoucha
et al., 2016; Feng et al., 2015; Gülen et al., 2015) contribute to the
adsorption of dyes by various binding mechanisms (Lee et al.,
 Y. Dai et al. / Chemosphere 211 (2018) 235e253
2015). Thus, ion exchange (Charles et al., 2016), complexation/co-
ordination (Ji et al., 2007), adsorption (Sharma et al., 2016), elec-
trostatic interaction (Safa, 2016), hydrogen bonding (Ahmad et al.,
2014) and p-p stacking interaction (Wang et al., 2017a,b) adsorp-
tion mechanisms have been proposed. Safa (2016) found that
mustard and linseed oil cakes can make use of electrostatic inter-
action to remove the acid dyes (Safa, 2016), and Marahel et al.
(2013) also found this mechanism when avocado integument
removed basic red 2 (BR2) dye (Marahel et al., 2013).
This section summarizes and comments on the application of
agricultural wastes in the preparation of adsorbents for adsorption
of organic pollutants from five aspects of dyes, drugs, pesticides,
aromatic compounds and oily substances.
4.1. Dyes
Growing demand for commercial dyes in various industries has
led to the mass production of dyes. More than 1.00  105 types of
commercial dyes are available, with annual output exceeding
7.00  105 tons, most of them are directly discharged into the
aqueous medium (Ansari et al., 2016). Water pollution can cause
numerous side effects such as mutagenicity, embryo toxicity,
teratogenicity and carcinogenicity as well as damage to the liver,
brain and central nervous and reproductive system resulting in
abnormal renal function (Tran et al., 2017a,b). Dyes in natural water
because of their content in aromatic hydrocarbons, metals, chlo-
rides can lead to reduced transparency, damage to photosynthesis,
damage to animals and plant growth, and affect the solubility of
oxygen and self-cleaning process (Bouguettoucha et al., 2016;
Tomczak and Tosik, 2017). And because of its high water solubility,
the dyes can be moved into the river affecting the water quality
(Dardouri and Sghaier, 2017).
In general, dyes are mainly anionic dyes (direct, acid and reac-
tive dyes), cationic dyes (alkaline dyes) and non-ionic dyes
(disperse dyes) (Chebli et al., 2015; Zhou et al., 2015). At present,
due to the harmfulness of dyes, many researchers are increasingly
concerned about the removal of dyes, they choose to use simple and
easy agricultural waste (such as: rice husk, straw, coconut shell,
olive powder) as adsorbent to study the removal of different types
of dyes.
4.1.1. Anionic dyes
Anion dyes is dependent on negative ions. They include many
compounds from different types of dyes, structural differences (azo,
anthraquinone, triphenyl methane and nitro dyes). For them,
however, there is a shared trait: water-soluble ionic substituents.
Acidic dyes, direct dyes and reactive dyes are anionic dyes (Zhou
et al., 2015).
4.1.1.1. Acid dyes. Acid dyes, acidic dyes have azo type, anthraqui-
none type, travel type, and most belong to azo dyes (https://baike.
so.com/doc/5630201-5842822.html). Such as naphthol blue black
(Palma et al., 2016), methyl orange (Hosseinzadeh and
Mohammadi, 2016; Mahmoud et al., 2017), acid blue 40 (Oei
et al., 2009), amido black 10B (Ojha and Bulasara, 2015). The
adsorption balance experiment was carried out by Safa (2015)
through studying the dissolution of the new biomass oil mustard
cake and flaxseed cake with Synolon black HWF-FS and Synolon
Red 3HF dye in batches. It found that the qm was 37.04 mg/g and
6.89 mg/g, respectively, and found its electrostatic interaction
mechanism (Safa, 2015). Lee et al. (2017) found that the qm of acid
blue 113 dye adsorbed by Cucumis serious skin was 59.80 mg/g
under the optimal conditions of pH 6.0 and temperature 323 K (Lee
et al., 2017). The studies show that agricultural waste is a friendly
and effective alternative to reduce the environmental pollution of
243
acidic dyes. Although there are not a few studies on this aspect, but
it need to pay more attention.
4.1.1.2. Direct dyes. The researchers explored the ability and
mechanism of using agricultural waste as an adsorbent to eliminate
direct dyes through various experiments. Among them, Chebli et al.
(2015) studied the use of a new low-cost disorient Stipa tenassi-
cima fibers that removed Congo red (CR) dye in aqueous solution,
studied the influencing factors and at pH 4.0, temperature 298 K
found that its qm was 7.93 mg/g. Its mechanisms of action were:
antiparticle diffusion, strong protonation and electrostatic in-
teractions (Chebli et al., 2015). Shang et al. (2015a,b) also tested for
CR adsorption by using polyethyleneimine-modified straw to
improve the adsorption capacity. The results showed that at 303 K,
its qm was 89.70 mg/g through the Langmuir model. And it found
that its mechanisms of action were mainly ion exchange and
hydrogen bonding (Shang et al., 2015a,b). In addition, direct dyes
include direct red 23 dyes (DR23). Fathi et al. (2015) evaluated the
applicability and efficiency of corn stover (CS) removal of DR23
using isotherms, kinetics and thermodynamic models and found it
was very effective. And it is good to conclude that CS was a friendly
adsorbent which removed DR23 and it was easy to get (Fathi et al.,
2015). According to different experimental studies, agricultural
waste can be used for direct dyes adsorption effectively (Chebli
et al., 2015). However, there is not much research on the adsor-
bent of agricultural waste as a direct dye, so more research is
needed.
4.1.1.3. Reactive dyes. Reactive dyes include reactive black 5 (RB5)
(Palma et al., 2016), reactive blue 5G (RB5G) (Mo
denes et al., 2015),
reactive red 141 (Sreelatha et al., 2011), and reactive blue 21
(Sreelatha et al., 2011). Researchers studied the adsorption perfor-
mance of different adsorbents on reactive dyes. For example, in the
case of RB5 adsorption, Palma et al. (2016) explored the production
of carbonaceous material in avocado skin by assessing the
carbonization temperature and time effect, and by acid, alkali,
reactive dye adsorption contrast, to explore the feasibility of
carbonization materials (Palma et al., 2016). However, Oei et al.
(2009) modified the barley straw by nitrogen adsorption, titration
and FTIR analysis, through the investigation of influencing factors
(adsorbent dosage, initial dye concentration, pH and temperature)
to find the most suitable conditions (Oei et al., 2009). Mo
denes et al.
(2015) studied the removal of RB5G by drying biomass of low cost
biosorbent prepared from banana pseudostem (BPS). The results
showed that the adsorption of RB5G dye was the process of physical
adsorption (Mo
denes et al., 2015). Reactive dyes are mainly used in
dyeing and printing of cotton, hemp, viscose, silk, wool and other
fibers and their blended fabrics, so for the removal of the research is
very important. Many studies have shown that agricultural waste,
as a simple biological adsorbent, can effectively remove reactive
dyes, but more research is needed (Palma et al., 2016).
4.1.2. Cationic dyes
Common cationic dyes include malachite green (MG) (Agarwal
et al., 2016; Ren et al., 2016), BR2 (Marahel et al., 2013), basic
blue 41 (Palma et al., 2016), crystal violet (Smitha et al., 2012; Wang
et al., 2017a,b), rhodamine B (Smitha et al., 2012; Wang et al.,
2017a,b), methylene green (Tran et al., 2017a,b) and MB (Djelloul
and Hamdaoui, 2015; Gülen et al., 2015; Zhu et al., 2016a,b,c,d).
Among them, MB is a cationic dye that researchers are more con-
cerned about, for example: using the rind as adsorbent to remove
MB (Djelloul and Hamdaoui, 2015), sumac leaves as a low cost and
effective biological adsorbent to remove MB (Gülen et al., 2015),
using citric acid to repair the gas tea as MB adsorbent (Zhou et al.,
244 Y. Dai et al. / Chemosphere 211 (2018) 235e253
2016). The experiment using different agricultural wastes as ad-
sorbents to adsorb MB concluded that the adsorption mechanism
were mainly electrostatic interaction (Gülen et al., 2015; Nayak and
Pal, 2017), particle internal diffusion (Gülen et al., 2015; Nayak and
Pal, 2017; Sharma et al., 2016; Zhu et al., 2016a,b,c,d; Zhou et al.,
2016), ion exchange (Nayak and Pal, 2017), boundary layer diffu-
sion (Nayak and Pal, 2017; Sharma and Tiwari, 2016; Zhu et al.,
2016a,b,c,d). In addition, Ren et al. (2016) used agricultural waste
garlic as a adsorbent to remove malachite green, through the
Langmuir model, and found that at pH 8.0, temperature 298 K,
adding 2.00  103 mg/L gallon particles, adsorption capacity was
the largest 232.56 mg/g. And it was proved that garlic root can be
used as adsorbent which is low-cost, and can be used to remove
dyes from industrial waste water (Ren et al., 2016). It is very
necessary to reduce the pollution of the environment in the age
when the dye is widely used. According to the recent research,
agricultural waste as an environment-friendly adsorbent can
effectively adsorb cationic dye. However, there is no reason to stop
exploring and further strengthen agricultural waste as adsorbents
for the removal of dyes.
4.1.3. Non-ionic dyes
Non-ionic dyes also refer to disperse dyes. At present, there are
few studies on the removal of non-ionic dyes from agricultural
wastes as adsorbents. Bamboo stalk as precursor, pretreated acti-
vated carbon (AC) by low-temperature chemical activation, and
used AC to remove azo disperse red 167 (Zhou et al., 2015). Dyes as a
substance that is colored and harmful to human, other animals and
plants, deserve greater attention from researchers. More agricul-
tural waste should be used to remove such substances as an
adsorbent. The corresponding adsorption parameters of dyes are
shown in Table 8.
4.2. Drugs
Drugs are dangerous environmental contaminants around the
world (Kyzas and Deliyanni, 2015). As a newly recognized category
of environmental pollutants, drugs have received considerable
attention in terms of their environmental fate and toxicological
nature (Kyzas and Deliyanni, 2015; Portinho et al., 2017). Drugs are
made by humans and animals, unchanged or in metabolite form
through urine and feces (Portinho et al., 2017). Drugs bring con-
venience to humans, but they also cause pollution, and improper
handling can lead to water, soil and other pollution. Therefore, the
treatment of drugs is particularly important, especially agricultural
waste as adsorbent to remove drugs. The studies show that agri-
cultural waste is an environmentally friendly adsorbent (Portinho
et al., 2017).
4.2.1. Antibiotics
Antibiotics can control infectious diseases and be used as feed
additives to promote healthy growth (Wang et al., 2017a,b). Since
the introduction of penicillin into drug therapy in 1942, hundreds
of other antibiotics have been isolated or synthesized for the
treatment of human and animal infections (Qiao et al., 2018). With
the increasing use of antibiotics, environmental problems have
gradually emerged. Researchers are also paying more attention to
the removal of antibiotics, which are the focus of researchers
attention by using agricultural waste as adsorbent to adsorb anti-
biotics. Yin et al. (2016) used iron ore to alter straw biomass (MSF)
to improve the ability of adsorbing the tylosin (TYL). The results
showed that the main adsorption mechanism was attributed to
electrostatic interaction and hydrophobic interaction, in addition, it
might be related to H-bonding and surface complexation. As a
result, MSF was considered to be the removal of TYL scavengers and
had great potential for removing organic contaminants from
aqueous solutions (Yin et al., 2016).
In antibiotics, tetracycline (TC) is a concern for researchers. TC is
one of the most widely used antibiotics and is often used in animal
husbandry (Wang et al., 2017a,b). Therefore, the removal of tetra-
cycline is very necessary. The study was designed to investigate the
feasibility of removing TC from rice husk ash (RHA) as a new
adsorbent, and the results showed that RHA was a cheap adsorbent
for removing TC and reached the qm 8.37 mg/g at 313 K. The
experiment was a magnetic carbon composite with layered struc-
ture, which was used to prepare TC adsorption of bagasse by hy-
drothermal carbonation and simple heat treatment process, the
magnetic carbon composites exhibited qm 48.35 mg/g, and the
chemical and mechanical properties were stable and the magnetic
properties were good. The adsorption of TC by magnetic adsorbent
was mainly attributed to H-bonding and a-b interaction. The results
showed that sugarcane bagasse in the sugar industry could be
effectively converted into magnetic adsorbent to remove TC by
environmental friendly methods (Rattanachueskul et al., 2016). The
use of agricultural waste to absorb antibiotics will have a great
impact on human development. Therefore, researchers should
devote more energy to the removal of antibiotics and other
methods to explore. The use of antibiotics is one of the greatest
advances in human history, but at the same time it has brought
harm to human beings and the environment. And if not governed,
there will be unimaginable crises. At present, there are many ex-
periments on the removal of antibiotics. Among them, agricultural
waste as adsorbent has brought hope to researchers, which will
have a great impact on human development. Although there are
many studies on the removal of antibiotics, researchers need to
explore more accurate and effective ways to mitigate environ-
mental pollution.
4.2.2. Other drugs
In addition to antibiotics, there are anti-inflammatory drugs
(diclofenac, ketoprofen, naproxen, nimesulide, ibuprofen, diclofe-
nac sodium) and other medications (Zhou et al., 2015). Portinho
et al. (2017) investigated the availability of caffeine from aqueous
solution on grape stalk, observed better adsorption ability in acidic
solution, assessed balance by adsorption isotherm structure, and
found the qm 916.70 mg/g (Portinho et al., 2017). As one of the most
dangerous contaminants, drugs need to be solved and removed.
Experimental study using various agricultural wastes to remove
drugs showed that agricultural waste is a good adsorbent and has
great potential. The corresponding adsorption parameters are
shown in Table 9.
4.3. Pesticides
Pesticides can kill organisms that cause disease and can prevent,
kill weeds, pests, fungi or microorganisms (viruses and bacteria)
(Trivedi et al., 2016). At present, the synthetic chemical pesticides
are about 500 species. The widespread use of these pesticides, not
only causes serious environmental pollution, but also hazards hu-
man health (https://zhidao.baidu.com/question/292778191.html).
Pesticides affect humans and the environment including air, soil
and water (Pen ~ a et al., 2016). As an effective method of pesticide
removal, adsorption is favored by researchers, especially agricul-
tural waste as adsorbent. For example, Ga
miz et al. (2016) investi-
gated how to repair agricultural soil with 2% of compost from olive
mill waste or its biochar (BC), affecting the adsorption, degradation
and leaching of two enantiomers of choral fungicide a cream. It
concluded that when BC was applied to soil, it can reduce pollution
in agriculture and reduce the mobility of highly polar chiral
 Y. Dai et al. / Chemosphere 211 (2018) 235e253 245

Table 8
Maximum adsorption capacity and mechanism of dyes on different agricultural wastes.

Agricultural waste Dyes pH Temperature qm(mg/ Sorption mechanism Reference

(K) g)

Camelina-derived Methylene blue 6.0 323 5.08 Intraparticle diffusion, Surface adsorption Sharma and Tiwari,
Sapindus-derived Methylene blue 6.0 323 50.76 2016
Sumac leaves Methylene blue 5.0 298 5.80 Chemisorption, Physisorption, Electrostatic Interactions Gülen et al., 2015
Linseed oil cake Synolon black 2.0 _ 6.89 Electrostatic Interactions Safa, 2016
HWF-FS
Mustard oil cake Synolon red 1.0 37.04
3HF
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 interaction, p-p Wang et al., 2017a,b
stacking interaction driven
Stem of Solanum tuberosum Malachite green 7.0 303 27.00 Physisorption Gupta et al., 2016
Methylene blue 41.60
Leaves of Solanum tuberosum Malachite green 33.30
Methylene blue 52.60
Sesame waste Reactive red 1.1 293 27.55 Electrostatic Interactions Sohrabi and Ameri,
141 2015
Bengal gram fruit shell (BGFS) Acid blue 25 2.0 308 29.41 Electrostatic Interactions, Intraparticle diffusion Krishna et al., 2017
Coconut coir dust Cationic dye 6.0 303 29.50 Interaction, Electrostatic force Etim et al., 2016
Cucumis sativus Crystal violet 7.0 300 33.22 Boundary layer diffusion, Intraparticle diffusion Smitha et al., 2012
Rhodamine B 35.33
Sulfuric acid-Cucumis sativus Crystal violet 6.3 300 40.82
Rhodamine B 34.01
Banana pseudostem Reactive blue 1.0 303 37.01 Ion exchange, Physisorption
denes et al., 2015
Mo
5G
Corn stalks Direct Red 23 3.0 318 51.87 Electrostatic Interactions Fathi et al., 2015
Water Bamboo Leaves Methylene blue 6.8 283 54.17 Intraparticle diffusion, Electrostatic Interactions Zhu et al., 2016a,b,c,d
Walnut Shell Methylene blue 6.0 318 56.13 Chemical reaction Tang et al., 2017a,b
Cucumis sativus peel Acid Blue 113 6.0 323 59.81 Chemisorption Lee et al., 2015
Rice straw-Microwave induced Methylene blue 7.0 298 62.50 H-bonding, Electrostatic attraction Mashhadi et al.,
-H2SO4 activation 2016a,b
Avocado integument BR2 dye 7.0 303 102.45 Ion exchange, Chemical reaction, Electrostatic Interactions, Marahel et al., 2013
Protonation of surface groups
Potato (Solanum tuberosum) peel Methylene blue 6.2 298 105.26 Physisorption, Electrostatic Interactions Guechi and
Hamdaoui, 2015a,b
Polyethyleneimine-modified Congo red 5.0 313 118.00 H-bonding, Van Der Waals, p-p conjugate, Ion exchange Shang et al., 2015a,b
wheat straw
Citric acid modified peanut shell Methylene blue 303 120.48 Electrostatic attraction Wang et al., 2015
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, p-p interaction Naushad et al., 2015
shells
Alfa grass Methylene blue 12.0 293 200.00 Ion exchange, Chemical reaction, Electrostatic Interactions, Toumi et al., 2015
External diffusion
Aminated pumpkin seed Methylorange 3.0 318 200.30 Electrostatic Interactions Subbaiah and Kim,
2016
Durian Seed - KOH Synthetic Dye 2.0 303 357.14 H-bonding Ahmad et al., 2014
Fe3O4-wheat straw Basic Blue 9 7.0 323 627.10 Complexes adsorption, Ion exchange, Deprotonation Pirbazari et al., 2014

Table 9
Maximum adsorption capacity and mechanism of other organic pollutants on different agricultural wastes.

Agricultural wastes Organic contaminants pH Temperature(K) qm(mg/ Sorption mechanism Reference

g)

Bagasse fly ash 2,4- 3.5 328 7.14 Van Der Waals Deokar et al., 2016
dichlorophenoxyacetic
acid
Typha orientalis Presl Phenol 5.0 313 7.23 Electrostatic Interactions, The sharing or exchange of Feng et al., 2015
electrons
Rice straw Tetracycline 5.5 298 14.16 p-p electron donor-acceptor, H-bonding, Hydrophobic, Wang et al., 2017a,b
Electrostatic interactions
Modified sugarcane bagasse Tetracycline 6.8 303 48.35 H-bonding, p-p interaction Rattanachueskul
et al., 2016
Rice husk Fluoroquinolone 5.1 309 63.50 H-bonding Ashrafi et al.,
NaOH-modified rice husk 241.00 2015a,b
Hazelnut shell derived Tetracycline (TC) 5.0 293 312.50 H- bonding, p-p electron donor-acceptor, pep dispersion Fan et al., 2016a,b
activated carbons Oxytetracycline (OTC) 322.60 interaction
Chlortetracycline (CTC) 333.30

miz et al., 2016). In addition, BC can be used as a fixed

pesticides (Ga ~ a et al. (2016) also conducted experi-
prevention strategies. Pen
correction in soil remediation and groundwater pollution ments on the adsorption of pesticides, which evaluated the effects
246 Y. Dai et al. / Chemosphere 211 (2018) 235e253
of de-oiled two-phase olive mill waste on the behavior of metri-
buzin in the Mediterranean agricultural soil and assessed the ef-
fects of these wastes on the conversion of organic matter in situ
conditions (Pen ~ a et al., 2016).
2,4-dichlorophenoxyacetic acid (2,4-D) is a systematic, selective
and popular herbicide and plant growth regulator, and is widely
used in broad-leaved plants worldwide. It is highly toxic and may
be harmful to humans and animals (Lo
pez-Cabeza et al., 2017). It
was also reported by the International Agency for Cancer Research
as carcinogenic and mutagenic agents (Trivedi et al., 2016). There-
fore, the removal of 2,4-D has become the focus of researchers. The
H3PO4 -activated langsat empty fruit bunch was used by Njoku et al.
(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 internal diffusion of parti-
cles was the main control mechanism (Njoku et al., 2015). Deokar
et al. (2016) used bagasse fly ash (BFA) as adsorbent to remove
2,4-D. The results showed that BFA can be an adsorbent which is
low cost and efficient (Deokar et al., 2016).
Pesticides are characterized by high efficiency and high residual
or low residue, among which many species have high acute toxicity
to mammals. So the hazards of pesticide use are not to be under-
estimated. Although researchers have done a lot of research on the
removal of pesticides, this is far from enough. In recent years, the
studies of agricultural waste as an adsorbent to remove pesticides
have brought dawn to the researchers, but further research is also
needed to achieve more efficient and accurate. The corresponding
adsorption parameters are in Table 9.
4.4. Aromatic compounds
Organic Pollutants in addition to dyes, pesticides, pharmaceu-
ticals and other organic compounds, there is a class of the material-
aromatic compounds that the researchers should pay attention to.
Many aromatic compounds contain a benzene ring, which binds to
one or more substituent groups (Ouellette and Rawn, 2015). Among
them, polycyclic aromatic hydrocarbon is a kind of matter of
concern. It is a toxic pollutant which is produced in the process of
fossil fuel combustion, which is a toxic, mutagenic, carcinogenic,
almost biodegradable organic compound (Kronenberg et al., 2017;
Lamichhane et al., 2017; Yang et al., 2017). Aromatic compounds are
classified by the United States Environmental Protection Agency
and the European commission (Gupta and Gupta, 2015). They can
be released in the water system through various sources, such as
industrial waste water, agricultural runoff and polluted air depo-
sition (Gupta and Gupta, 2015). And they pose a great threat to the
human body and the environment. Gupta and Gupta (2015) syn-
thesized activated carbon from waste banana peel, aimed to
remove polycyclic aromatic hydrocarbons from the water system,
established Langmuir and Freundlich model, and calculated char-
acteristic parameters of adsorption isotherm. It concluded that the
adsorbent prepared from banana peel can be easily used in in-
dustrial processing plants to remove polycyclic aromatic hydro-
carbons (Gupta and Gupta, 2015). And the authors found that the
removal of sugar or hydrolytic biomass was a promising biological
adsorbent for the removal of polycyclic aromatic hydrocarbons
(Tran et al., 2015).
In addition, aromatic compounds include phenols and their
derivatives (phenol, chlorophenol, para-chlorophenol, ortho-
Chlorophenol). Phenolic compounds have a water-soluble, highly
toxic, adverse impact on aquatic organisms and the environment
(Karri et al., 2017). Phenolic compounds are highly mobile and
soluble in water capacity, which can be mixed by natural drinking
water downstream, causing serious harm and health hazards to the
human body (Karri et al., 2017). Therefore, the treatment of
phenolic compounds and their compounds is the key to ensure
environmental and human health. At present, many researchers
have carried out studies on the removal of phenolic compounds
from agricultural wastes as adsorbents, and the main adsorption
mechanisms are hydrogen bonding, hydrophobic interaction, p-p
interaction, ion exchange, electronic sharing and exchange, elec-
trostatic interaction, boundary layer diffusion, particle internal
diffusion (Feng et al., 2015; Shah et al., 2016; Tonucci et al., 2015;
Tran et al., 2015). Feng et al. (2015) passed from cattails (Asha
Orientalis Presl)preparation of activated carbon and evaluated the
ability of removing phenol, and the adsorption experiment found
that the ionic strength of the effect of phenol removal was minimal,
and concluded that Asha Orientalis Presl has great potential, and
was an economic and effective adsorbent (Feng et al., 2015).
Aromatic compounds, which are characterized by stable struc-
ture, easy decomposition and strong toxicity, cause serious pollu-
tion to the environment and cause great harm to human body.
Therefore, the study of its removal is particularly important. In
recent years, researchers have done a lot of research, in which
agricultural waste as adsorbent to remove aromatic compounds is a
friendly and effective method. For its removal, there have been
great achievements. But researchers cannot stop there and should
continue to explore ways to be more efficient and green and apply
them to industry. The corresponding adsorption parameters are
shown in Table 9.
4.5. Oil substances
Oil pollution poses a serious threat to the environment. When
oil floating into water, it can spread hundreds of miles, form thin
layers and prevent oxygen moving from the atmosphere to aquatic
organisms (Abdelwahab et al., 2016). The largest source of pollution
is oil substances (Zhou et al., 2015). In recent years, more and more
research has focused on agricultural waste as an adsorbent to
remove oil, such as barley straw, coconut shells, garlic and onion
skins (Ibrahim et al., 2010; Zhou et al., 2015). Abdelwahab et al.
(2016) modified the bagasse by esterification and coating of poly-
acrylonitrile and used as a hydrophobic adsorbent to remove diesel
from man-made seawater. The adsorption mechanism is chemical
adsorption, and it found that the maximum absorption of oil on all
adsorbents can be arranged as follows: paraffin oil > vegetable
oil > diesel oil > petrol. The results showed that the prepared
adsorbent can be actively involved in solving environmental
problems (Abdelwahab et al., 2016). In addition to petroleum
products, emulsified oil is also a material affecting the environ-
ment. Pachathu et al. (2015) studied the modified bagasse and
straw as emulsified oil absorption agent through the microwave-
assisted technology. Under 313 K, the maximum oil removal ratio
of microwave-assisted bagasse and straw were 98.07% and 98.72%,
respectively. It can be seen that the qm of modified bagasse and rice
straw were 192.58 mg/g and 276.82 mg/g, respectively. The
research results showed that agricultural waste can be used as an
effective adsorbent for oil products. In recent years, the study on
the adsorption of oil substances by agricultural waste as adsorbent
was not much, so it should be further studied.
4.6. Adsorption mechanisms for organic pollutant removal
The adsorption mechanism of organic pollutant removal de-
pends on the nature of the pollutant and the chemical properties of
the agricultural waste surface (Rosales et al., 2017). And it is also
accompanied by a variety of factors that affect each other. In the
batch mode, the adsorption experiment of the polyethyleneimine-
modified wheat straw (NWS) on CR was carried out by Shang et al.
(2015a,b). The experiment has shown that in NWS there were
 Y. Dai et al. / Chemosphere 211 (2018) 235e253 247

varieties of floristic fibers and some functional groups including

carboxyl, hydroxy and amides, which can be used for adsorption
process. H-bonding was the principal adsorption mechanism of the
adsorption process, and it also accompanied with a variety of
mechanisms (Shang et al., 2015a,b). Wang et al. (2017a,b) studied
the adsorption of tetracycline by activated carbon prepared by
straw at different temperatures and found that the pep electron-
donor acceptor and the high surface area of the biochar samples
derived from rice straw that were pyrolyzed at 973 K made its high
adsorption capacity (Wang et al., 2017a,b). Scholar studied the
magnetic composite materials prepared by bagasse to remove
tetracycline, and found that the oxygen-containing functional
groups on the surface of the adsorbent played a dominant role in
the adsorption of TC. The oxygen-containing groups on the com-
plex adsorbent and the -OH, C¼O and -NH2 on the TC molecule
form H bonds. In addition, the surface of the composite has a
partially aromatic characteristics, indicating that an electron donor-
acceptor (EDA) interaction, or cation-bonding, can form a cationic
bond with the conjugate in the TC molecule ring. The specific
mechanism of the adsorbent and TC is shown in Fig. 6
(Rattanachueskul et al., 2016). Shah et al. (2016) studied the
adsorption of chlorine-chlorophenol on zeolite composites derived
from bagasse fly ash. The experimental results shown that the Fig. 7. The adsorption mechanism of organic pollutants on agricultural waste.
adsorption process were dominated by p-p interaction and affinity
formation of donor acceptor complexes on the adsorbent surface are different, which results in different mechanisms of the
(Shah et al., 2016). Electrostatic effect is also the main mechanism adsorption organics by various agricultural wastes (see Fig. 7). In
of agricultural waste adsorption organic pollutants. Many re- this paper, the qm and mechanisms of agricultural waste under
searchers had come to the same conclusion by experiments (Fathi different experimental conditions are listed.
et al., 2015; Krishna et al., 2017; Mashhadi et al., 2016a,b). In
addition, Deokar et al. (2016) used bagasse fly ash as an adsorbent
to remove 2,4-dichlorophenoxyacetic acid. The result shown that 5. Get rid of the gas
the molecules form of 2,4-D mainly due to Van Der Waals inter-
action was adsorbed on the surface of BFA, while the anionic form With the increasingly serious environmental problems, in
may be due to electrostatic interaction was adsorbed (Deokar et al., addition to inorganic and organic pollutants, harmful gases have
2016). Fan et al. (2016a,b) used the activated carbon derived from become the focus of global attention. At present, global warming
hazelnut shell to remove tetracycline antibiotics, indicating that and climate change are already a major threat to human survival,
electron donoreacceptor, hydrogen bonding, and p-p dispersion and human beings are facing melting glaciers, rising sea levels and
interaction between the aromatic ring of three antibiotics are the other problems. The rapid increase of greenhouse gases is one of
main adsorption mechanisms. And the kinetic analysis shown that the reasons. Two main types of greenhouse gases include carbon
the adsorption process can ascribe to external transfer and intra- dioxide (CO2) and nitrous oxide (N2O). In 2017, the concentration of
particle diffusion (Fan et al., 2016a,b). On the other hand, the CO2 in the atmosphere was 406 mg/L (Ramphull and Surroop,
adsorption mechanism of MB onto adsorbent including physical 2017).
adsorption and chemical adsorption was studied (Fan et al., Excessive CO2 stimulates the human respiratory center, causing
2016a,b). Due to the different chemical composition of various shortness of breath and headaches, confusion and other symptoms.
agricultural wastes, the surface active groups and functional groups N2O greenhouse effect was about 300 times serious than CO2 (Yin
et al., 2016). Dizziness, loss of direction and balance, memory

Fig. 6. The adsorption mechanism of TC on a magnetic composite derived from sugarcane bagasse.
(Rattanachueskul et al., 2016).
248 Y. Dai et al. / Chemosphere 211 (2018) 235e253
loss, cognitive impairment, and weakness in the legs are all the side
effects of N2O. Severe or prolonged use of N2O can cause vitamin
B12 inactivation, leading to functional vitamin B12 deficiency,
initial finger numbness, and possibly further development of pe-
ripheral neuropathy and giant cell anemia (Amsterdam and
Nabben, 2015). Currently, research on greenhouse gases mainly
focuses on the capture and storage of gas. In recent researches,
adsorption has the characteristics of high efficiency and low
pollution, so it is a suitable technology for this pollution. Moreover,
biochar is a cheap and easily available adsorbent. Nowadays, many
agricultural wastes are used for adsorb harmful gases. Through the
activation of CO2, ammonification with ammonia (NH3) and the
treatment of soybean straw with CO2 and NH3 at high temperature,
Zhang et al. (2016b) found that the optimum activation conditions
were obtained and the qm was 49.87 mg/g (Zhang et al., 2016c). Erto
et al. (2016) pointed out that the removal of CO2 by pyrolysis and
steam-activated agricultural waste mainly relied on the high
micropore volume and narrow pore size distribution (Erto et al.,
2016). Shahkarami et al. (2015) identified the main differences of
the surface chemistry, porous structure and morphology of acti-
vated carbon obtained through rapid and slow pyrolysis of agri-
cultural waste, and obtained the qm 78.10 mg/g (Shahkarami et al.,
2015). A research about the adsorption of 16 volatile organic
compounds in the gas phase by activated carbon from waste rice
hulls, and proposed the adsorption mechanism were hydrogen
bonding and non-specific interaction (Li et al., 2016). Scholar also
made use of rice husk as adsorbent, and developed an effective
adsorbent of flue gas removal by modification (Zhu et al.,
2016a,b,c,d). These studies show that agricultural waste can play
a significant role in the removal of greenhouse gases, and its
adsorption mechanism mainly depends on the high micropore
volume, narrow pore size distribution, hydrogen bonding and non-
specific interaction. Harmful gases in a certain extent will endanger
the survival of mankind. The problem of accumulation for agri-
cultural wastes is also urgent to be solved. The use of waste as an
adsorbent to remove greenhouse gases can solve both problems.
However, there are still few researches in this area, which still need
to be further explored by researchers.
6. Application of adsorbents in engineering
6.1. Adsorption in liquid phase
The use of agricultural waste as adsorbent for fixed bed ad-
sorbers removes organic substances in water, and is often used in
Fig. 8. Typical fixed-bed adsorbers in water treatment: (a) pressure GAC filter made of corrosion-resistant steel and (b) rectangular gravity concrete filter.
(Worch, 2012).
drinking water treatment, groundwater remediation, and swim-
ming pool water treatment (Shao, 2013). The current adsorber for
treating the water phase is designed as a closed pressure filter or an
open gravity filter. The material of the filter is usually corrosion-
resistant steel or concrete. The adsorbent in a fixed bed adsorber
is located at the bottom of the perforation, and water typically
flows down through the adsorbent bed. Between the activated
carbon and the bottom there is a small layer of sand used to remove
the toner(see Fig. 8). As the most common adsorbent for water
treatment, agricultural waste exists in two forms: powdered and
granular. Granular agricultural waste is used in fixed bed adsorbers.
In a wastewater treatment plant, multiple adsorbers in series
can make the fixed bed adsorption process a continuous process,
reducing capacity loss. In principle, there are two ways to connect a
single fixed bed adsorber to a multiple adsorber system: series and
parallel. The total sorbent mass was divided into four adsorbers,
only three adsorbers were running, and the other was stopped to
regenerate the adsorbent. The time t1 indicates the time point at
which the adsorber 1 is inactive and the mass transfer zone (MTZ)
is located between the adsorbers 3 and 4. As the MTZ has left the
adsorber 2, the adsorbent in the adsorber is fully saturated to
equilibrium. Therefore, the adsorber 2 will be the next stop. The
time t2 indicates a later time. So on and so forth. In an ideal situ-
ation, all adsorbers can be operated until the entire adsorbent bed
reaches the equilibrium load. The total flow to be treated is divided
into a plurality of substreams which are supplied to a plurality of
adsorbers operating in parallel. Different adsorbers are put into use
at different starting times. Therefore, at a given time, the travel
distance of MTZ in different adsorbers is different, so the break-
through time is also different. Different concentrations of different
sorbent effluents are mixed to obtain a total effluent stream. The
main advantage of parallel connections is that the total cross-
sectional area increases with the number of adsorbers. Therefore,
this multi-adsorber system is very flexible and can be adjusted
according to the different requirements of the amount of water that
needs to be treated. It is particularly suitable for handling large
amounts of water.
6.2. Adsorption in the gas phase
The use of bio-carbon derived from agricultural waste such as
sugarcane bagasse (Youssef, 1981) as Carbon Molecular Sieve (CMS)
to isolate gas is another important application of agricultural waste
in industry. Researcher found three fluxes in the hole through the
“selective surface Flow” carbon film: flux, Knudsen flux, and
 Y. Dai et al. / Chemosphere 211 (2018) 235e253
Fig. 9. Schematic of exclusive surface diffusion CMS membrane.
(Golden et al., 1998).
diffusion through the surface (Rao and Sircar, 1993). Surface diffu-
sion can be the main flux of pore diffusion when the surface con-
centration is high or when other fluxes are low (Kapoor et al., 1989).
Moreover, when the pore size is about twice times that of the
strongly adsorbed molecule, the adsorbed molecule effectively re-
duces the pore openings, thereby eliminating or hindering the
fluxes of other adsorbed or weakly adsorbed molecules, and
eventually enhancing the separation. The successful application of
the separation principle depends on the fabrication of a membrane
with controllable and uniform aperture, through the poly (two)
vinyl chloride controlled pyrolysis experiment supported on the
macroporous alumina tube(Golden et al., 1998). The principle of
CMS membrane is shown in Fig. 9 (Golden et al., 1998).
CMS membrane has a relatively unique distribution of molec-
ular size of the membrane hole, good separation and mechanical
properties as well as high stability. Therefore, the CMS membrane
can be used in air O2/N2 separation, H2 recovery, CO2 enrichment,
low carbon hydrocarbon separation and He recovery, and has a
good application prospects.
7. Adsorbent regeneration
The study of adsorbent regeneration can effectively prevent
secondary pollution caused by waste adsorbents (Anirudhan and
Sreekumari, 2011). At present, commonly used adsorbent regen-
eration methods include solvent extraction, calcination, and bio-
logical methods. The solvent extraction method uses an
appropriate solvent to extract the adsorbate from the adsorbent.
The calcination method is to adsorb the adsorbed adsorbent at a
high temperature to convert the adsorbate into a gas or a volatile
substance, thereby recovering the adsorbent's adsorption capacity.
Emerging bioremediation utilizes microorganisms to desorb the
adsorbent and achieve desorption and regeneration of the adsor-
bent, which is characterized by simple operation, low cost, and low
environmental impact (Zhang et al., 2009).
In the experiment, hydrochloric acid, sulfuric acid, and nitric
249
acid are commonly used to desorb the heavy metal ions adsorbed
by the biomass adsorbent by placing an adsorbent that has adsor-
bed heavy metal ions in an acidic solution and competitively
adsorbing the heavy metal ions by Hþ ions to make the heavy metal
ions. Replace it for regeneration. The experiment was carried out by
using 0.1 mol/L hydrochloric acid to desorption of algae Oedogo-
nium sp. which adsorbed Cd2þ. The adsorption capacity of algae in
4 cycles was 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 study
was carried out used a 0.1 mol/L hydrochloric acid solution as a
desorption agent. The desorption humic acid adsorbent was acti-
vated with 0.1 mol/L NaOH solution, and then the adsorbent was
washed with ultrapure water. The next cycle of adsorption exper-
iments was performed with propargite adsorbents. Repeatedly for
5 cycles, the adsorption of Cd2þ were 20.12 mg/g, 19.35 mg/g,
18.96 mg/g, 18.52 mg/g, and 18.13 mg/g, respectively (Chen et al.,
2014). It can be seen that the biomass adsorbent can be used
repeatedly and has good practical application value.
8. Future perspectives
At present, China is the country with the largest output of
agricultural waste all over the world. When its agricultural waste in
the process of not being effective use, to a certain extent, increased
the burden of rural agricultural production, more importantly, also
caused the pollution of the rural environment. Therefore,
increasing the reuse of agricultural wastes can effectively reduce
the air pollution caused by plant incineration. The soil pollution
caused by the residues of heavy metals and pesticides in plants,
fixed N/P to replenish soil nutrients and improve soil quality of
cultivated land. Meanwhile, it also can prevent the water pollution
caused by livestock manure and the spread of bacteria and viruses
caused by the long-term decay of agricultural wastes, and improve
the ecological environment (Liu, 2017).
From domestic and international studies, it can be seen that
agricultural waste is an ideal choice to deal with pollutants and
250 Y. Dai et al. / Chemosphere 211 (2018) 235e253
improve its adsorption effect by modifying their properties. How-
ever, researchers often ignore the size of environmental pollution
caused by the modification process, the complexity of the modified
process and the level of the modified cost. Biochar is an idiographic
renewable resource and has great potential to solve several envi-
ronmental problems in recent years, including remediation of
contaminants in soil, water and gaseous media (Rosales et al.,
2017). The utilization of agricultural wastes for bio-carbon is the
core international competitive technology of green low-carbon
agriculture, which is the current international agricultural soil
carbon sequestration, waste environmental management, resource
recycling and energy saving and emission reduction, and tackling
climate change. This technology is to research and develop various
types of carbonization technology of agricultural waste biomass
and promote the industrialization of biochar, which can effectively
alleviate a series of realistic ecological and environmental prob-
lems, such as the increase of carbon emissions caused by the rapid
economic development, the increase of environmental pollution
and the increase of greenhouse gas emissions.
This paper argues that the future directions of agricultural waste
as adsorbent are:
(1) Research and develop of agricultural waste biomass
carbonization technology to promote the industrialization of
biomass carbon.
(2) Development of high efficiency green modifier and modifi-
cation process will be the development direction of biolog-
ical adsorption.
(3) Future research should also extend to the use of agricultural
waste adsorbents to deal with the engineering problems of
pollution scaling.
In summary, biomass adsorbents based on agricultural waste
show significant advantages and can be used to replace expensive
commercial activated carbon for environmental pollution control.
This provides a broad application prospect for the utilization of
agricultural waste.
9. Conclusions
With the development of economy, regional environmental
pollution and large-scale ecological destruction have become
increasingly serious, threatening the survival and development of
all mankind. Wide range of sources, low-cost, renewable bio-
sorbents is becoming more and more popular. Agricultural wastes
with loose and porous structure contain carboxyl, hydroxyl and
other active groups, which can remove pollutants better. Its
adsorption is effected by the pH, temperature, initial concentration
and other factors. Modified agricultural waste can get a better
adsorption effect. Its main mechanisms of adsorbing pollutants are
ion exchange, electrostatic interaction, complex adsorption and
others are still under further exploration. This paper believes that
the development of efficient green modifier and technology will be
the development direction of biological adsorption. Using agricul-
tural waste as biomass adsorbent can not only reduce the envi-
ronmental burden but also achieve the goal of “treating waste by
waste”. In the future environmental governance, it will have broad
space for development.
Acknowledgement
This work was supported by Program of Student Innovation
Practice Training (SIPT) of Northeast Agricultural University
(201810224031; 201810224356; 201810224357).
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