Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Contents lists available at ScienceDirect

Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Review

Recent advances on the adsorption of herbicides and pesticides from

polluted waters: Performance evaluation via physical attributes
Joshua O. Ighaloa,b , Adewale George Adeniyia , Adedeji A. Adelodunc,d,*
a
Department of Chemical Engineering, Faculty of Engineering and Technology, University of Ilorin, Ilorin, Nigeria
b
Department of Chemical Engineering, Nnamdi Azikiwe University, P. M. B. 5025, Awka, Nigeria
c
Environmental Engineering and Management Research Group, Ton Duc Thang University, Ho Chi Minh City, Viet Nam
d
Faculty of Environment and Labour Safety, Ton Duc Thang University, Ho Chi Minh City, Viet Nam

A R T I C L E I N F O A B S T R A C T

Article history: Due to the need to ameliorate the incessant presence of herbicides and pesticides (H & P) in our waters,
Received 19 February 2020 we appraised the recent advances in using adsorption technology. Of the numerous adsorbents,
Received in revised form 5 October 2020 montmorillonite and activated carbon (AC) cloth showed the highest adsorption capacity (q) of 1067 and
Accepted 7 October 2020
421.6 mg/g for 2,4-D herbicide and aldicarb, respectively. However, atrazine and aldrin (the most
Available online 14 October 2020
researched H & P, respectively) were best removed using eucalyptus bark-derived biosorbent (936.1 mg/
g) and acid-treated patellidae shells (208.3 mg/g), respectively. We carried out further investigation into
Keywords:
two newly derived adsorption attributes (effective surface area (eSBET) and preferential adsorption (qp).
Preferential adsorption
Effective surface area
The eSBET correlates more strongly with q than the conventional specific surface area (SBET) because
Herbicides surface chemistry influences the former. Likewise, qp is a more reliable attribute than q because qp
Pesticides considers the adsorbent's chemical properties and adsorbate’s solubility. The correlation between eSBET
Water pollution and qp was strongest for 2,4-D (95%) and AC (62.25%). Future research could use spent heavy metal
Surface chemistry adsorbents and photo-assisted adsorption to improve the removal of competitive adsorptives (H & P).
Conclusively, adsorption is excellent for mitigating H & P pollution, and the novel adsorption attributes
provided here would aid more liable performance optimization.
© 2020 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Contents

Introduction . . . . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118

Recent advances on H & P adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
Herbicides . . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
2,4-D . . . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
Ametryn . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Amitrole . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Atrazine . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Bentazon . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Diquat . . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
Diuron . . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Fenuron . . .. ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Glyphosate . ............. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

Abbreviations: 2,4-D, 2,4-dichlorophenoxyacetic acid; 2,4-DP, (R)-2-(2,4-dichlorophenoxy) propanoic acid; 2,4,5-T, 2,4,5-trichlorophenoxyacetic acid; AC, activated
carbon; CTAB, cetyltrimethylammonium bromide; DDS, dodecyl sulfate; DNA, dioxyribonucleic acid; EDC, endocrine-disrupting chemical; EFB, empty fruit bunch; eSBET,
effective surface area; IUPAC, International Union of Pure and Applied Chemistry; H & P, herbicides and pesticides; MWCNTs, multiwalled carbon nanotubes; MCPA, 2-methyl-
4-chlorophenoxyacetic acid; mCPP, chlorophenylpiperazine; pHzc, point of zero charge; q, adsorption capacity; qp, preferential adsorption; RMM, relative molecular mass; SN,
serial number.
* Corresponding author.
E-mail address: adedeji.adelodun@tdtu.edu.vn (A.A. Adelodun).

https://doi.org/10.1016/j.jiec.2020.10.011
1226-086X/© 2020 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Isoproturon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
Linuron . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
MCPA . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124
mCPP . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Metribuzin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Paraquat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Other herbicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Pesticides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Aldrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
Carbaryl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Deltamethrin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 128
Diazinon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Imidacloprid . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Oxamyl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Triadimenol . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Secbumeton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Mechanism of H & P adsorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
Performance evaluation: effect of sorbate-sorbent interphase . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Research trends and future perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Author contribution statement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Compliance with ethical standards . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Funding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Conflict of interest . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135

Introduction unfit for human consumption. Fig. 3 illustrates the routes and fate
of discharged pesticides into the aqueous environment. These
Pests and diseases account for about one-third of global crop emerging contaminants in the aqueous environment have led to
loss [1]. Therefore, herbicide and pesticides (H & P) are vital to environmental pollution and degradation [3,4].
producing arable crops. Fig. 1 summarises the annual average of Water pollution is the major environmental problem of the 21st
pesticide use intensity on croplands between 1990 & 2014. century, aside from climate change [5,6]. Due to water pollution
Further, the average quantities of pesticides used between 1990 that arises from exposure to these chemicals, researchers have
and 2014 in selected countries have been reported (Fig. 2a). We evaluated various remediation techniques. Researches have
observed that pesticide use has been on the rise in most countries. concluded that mitigation is essential before the environmental
Therein, the USA was notably excluded because of the excessively release of the contaminants [7].
large quantities associated with the nation. Exclusively, Fig. 2b Major remediation techniques include containment (process
depicts the quantities of pesticide (breakdown by types) used in and equipment modification, abandonment), separation (adsorp-
the USA between 1990 and 2007. tion, condensation, membrane filtration) [8–11], and destruction
Due to their continuous use, H & P get into water bodies by (biofiltration, chemical/photochemical/plasma oxidation) [12–14]
leaching, sub-surface drainage, and run-off, rending the waters technologies. Based on its intrinsic excellence ability for

Fig. 1. The annual average of pesticide use intensity on croplands between 1990 & 2014 [2].

118
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Fig. 2. Average pesticide consumption by (a) selected countries between 1990 and 2014, and (b) the United States of America between 1990 and 2007, with the breakdown by
type [2].

controlling pollutants at trace levels, adsorption has been studied

Fig. 3. Pathways of pesticides in the environment through the hydrological cycle
(Wikimedia Commons, 1999).
extensively amongst the available techniques. Both organic [15–18]
and inorganic-based adsorbents [19–21] have been reportedly
used for this purpose.
In a recent review, Cosgrove et al. [1] examined the mechanisms
of pesticide release into watercourses and the physicochemical
properties that control their retention in the aquatic environment.
Earlier, Foo and Hameed [5] had focused on the detoxification of
pesticides using activated carbon (AC)-based adsorbents. Both
studies focused on pesticides only. However, Mojiri et al. [22]
examined the critical factors that influence H & P adsorption.
In this current review, we describe each H & P and their
ecotoxicity, providing a broader and deeper focus on the recent
mitigation advances using various adsorbents. We focused on
contemporary literature published in the past decade and base our
discussions on the chemicals’ peculiarities. More importantly, we
provide novel assessments of the adsorbents’ performances via the
calculation of newly conceived physical attributes, which inform
the influence of the adsorbents’ physical and chemical properties
and the adsorbates on the separation process. Consequently, the

119
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 1
Names and attributes of some common herbicides reviewed in current work.

S/N Herbicides IUPAC name Chemical structure Molecular mass Specific Solubility in Melting
(g mol
1) gravity water point (oC)
1. 2,4-D 2,4-Dichlorophenoxy-acetic acid 221.03 1.42 0.54 g/l (at 140.5
20  C)

2. Ametryn 2-[Ethylamino]-4-isopropylamino-6-methyl-thio- 227.33 1.18 0.29 g/l (at 88
89

s-triazine 25  C)

3. Amitrole 3-Amino-1,2,4-triazole 84.08 1.138 280 g/l (at 159

20  C)

4. Atrazine 2-Chloro-4-ethylamino-6-isopropylamino-s- 215.69 1.187 0.7 g/l (at 175

triazine 20  C)

5. Bentazon 3-Isopropyl-1H-2,1,3-benzothiadiazin-4(3H)-one 240.3 1.41 0.57 g/l (at 138

2,2-dioxide 20  C)

6. Diquat 1,10 -Ethylene-[20 ,20 -dipyridylium] dibromide 184.24 1.22 708 g/l (at 337
monohydrate 20  C)

7. Diuron 3-[3,4-(Dichlorophenyl)-1,1dimethylurea] 233.09 1.48 42 mg/l (at 158

20  C)

8. Fenuron 1,1-Dimethyl-3-phenylurea 164.20 1.13 3.8 g/l (at 133

20  C)

9. Glyphosate N-[Phosphonomethyl] glycine 169.07 1.704 10.1 g/l (at 184.5

20  C)

10. Isoproturon 3-[4-Isopropylphenyl]-1,1-dimethylurea 206.28 1.2 70.2 mg/l (at 158

20  C)

11. Linuron 3-[3,4-Dichlorophenyl]-1-methoxy-1-methylurea 249.09 1.49 0.075 mg/l 93

(at 20  C)

120
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 1 (Continued)
S/N Herbicides IUPAC name Chemical structure Molecular mass Specific Solubility in Melting
(g mol
1) gravity water point (oC)
12. Metribuzin 4-Amino-6-[2-methyl-2-propanyl]-3- 214.29 1.28 1.2 g/l (at 126
[methylsulfanyl]-1,2,4-triazin-5(4H)-one 20  C)

13. MCPA 4-Chloro-2-methylphenoxyacetic acid 200.62 1.18 0.825 g/l (at 114
118
23  C)

14. mCPP 2-[2-Methyl-4-chlorophenoxy] propionic acid 214.65 1.28 0.88 g/l (at 94
95
25  C)

15. Paraquat 1,10 -Dimethyl-4,40 -dipyridinium dichloride 257.16 1.25 700 g/l (at 175
180
20  C)

16. 2,4,5-T 2,4,5-Trichlorophenoxyacetic acid 255.48 1.8 Insoluble 153
158

17. Chlorsulfuron 1- (2-Chlorophenylsulfonyl) -3- (4-methoxy-6- 357.77 – 0.125 g/l (at 176
methyl-1,3,5-triazin-2-yl) -urea 25  C)

18. 2,4-DP (R)-2-(2,4-Dichlorophenoxy) propanoic acid 235.064 1.42 0.72 g/l (at 117
122
20  C)

19. Imazethapyr 5-Ethyl-2-(4-isopropyl-4-methyl-5-oxo-4,5- 289.33 1.35 0.12 g/l (at 171

dihydro-1H-imidazol-2-yl) nicotinic acid 25  C)

adsorbents’ performance evaluation via statistical extrapolations is
also reported. Thence, this review comes at a crucial time when
research efforts to achieve environmental sustainability are rising
[23–25].
Recent advances on H & P adsorption
In this section, a case by case discussion of the recent
advances in herbicide and pesticide adsorption from aqueous
solution is presented. The chemical structure and properties of
common herbicides and pesticides are summarized in Tables 1
and 2, respectively. The recent advances are discussed, and the
literature presented is mainly published within the past
decade.
Each compound’s properties play a vital role in the nature and
rate of the adsorption process [26]. This review also pays special
attention to how the adsorbate-adsorbent interaction affects the
sorption of the pollutants. Much of the attributions are based on
pH, pH at point of zero charge (pHpzc), temperature, and the
general ionic properties of both sorptive and adsorbent. Though
the term pesticide is generic, and herbicides are considered a type
of pesticide (when weeds are regarded as pests), they were

121
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 2
Names and attributes of some common pesticides reviewed in current work.

S/N Pesticide IUPAC name Chemical structure Molecular Specific Solubility in water Melting
mass gravity point (oC)
(g mol
1)
1. Aldrin 1,2,3,4,10,10-Hexachloro-1,4,4a,5,8,8a-hexahydro- 364.9 1.6 Slightly soluble, 104
1,4:5,8-dimethanonaphthalene about 0.027 mg/l (at

27 C)

2. Carbaryl 1-Naphthyl methylcarbamate 201.225 1.2 0.11 g/l (at 22  C) 142

3. Deltamethrin [(S)-Cyano-(3-phenoxyphenyl)-methyl] (1R,3R)-3- 505.21 1.5 Insoluble (at 20  C), 98

(2,2-dibromoethenyl)-2,2-dimethyl-cyclopropane-1- <0.002 mg/l (at
carboxylate 25  C)

4. Diazinon o, o-Diethyl o-[2-isopropyl-4-methyl-6-pyrimidyl] 304.34 1.116 1 g/l (at 24  C) <25

phosphorothioate

5. Imidacloprid N-[1-([6-Chloro-3-pyridyl] methyl)-4,5- 255.66 1.6 0.51 g/l (at 20  C) 136.4

dihydroimidazol-2-yl] nitramide

6. Oxamyl N,N-Dimethylcarbamoyloxyimino-2-[methylthio] 219.26 0.97 0.28 g/l (at 25  C) 100
102

acetamide

7. Triadimenol 1-(4-Chlorophenoxy)-3,3-dimethyl-1-[1,2,4]triazol-1- 295.76 1.24 0.12 g/l (at 20  C) 125

yl-butan-2-ol

8. Secbumeton 2-N-Butan-2-yl-4-N-ethyl-6-methoxy-1,3,5-triazine- 225.29 1.1 Insoluble 87.0

2,4-diamine

categorized separately in this review because the herbicides are
used on plants alone.
Herbicides
2,4-D
2,4-Dichlorophenoxyacetic acid is one of the most commonly
used herbicides against broadleaf weeds and pests [27]. The
compound possesses some grave eco-toxicological effects on
humans and animals. In humans, it can lead to intellectual
disability, miscarriage, defects in tissues, failure of the central
nervous system, failure of the liver, ear damage, and other
teratogenic and carcinogenic effects [27,28].
Abdeldaiem et al. [29] studied the sorption capacity (q) of 2,4-D
by commercial activated carbons (AC) obtained from maritime
pine wood, chemically activated with phosphoric acid (1.56 mmol/
g) and those from steam activation of peat (1.49 mmol/g). Due to its
negative charge in acidic solutions, 2,4-D electrostatically interacts
with the adsorbent's positively charged surface. However, the
presence of two electron-withdrawing chloride groups weakens
the dispersive interactions between p-electrons of the aromatic
ring of the pollutant and those of the graphene planes of the

122
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
adsorbents. In another recent study, Chair et al. [30] evaluated the
bio-adsorption and photo-electrochemical oxidation of soil
washing effluent contaminated with 2,4-D. They observed a q
value of 0.012 mg/g using activated sludge from a water treatment
facility. As part of their investigation, the study provided a
performance evaluation of photo-electrolysis of electrolysis for the
specific application. More recently, De Souza et al. [27] achieved an
adsorption capacity of 50.36 mg/g on organo-modified bentonite
clay. The study further buttressed the regeneration-reusability
merit of the adsorbent. It was revealed that up to 95% of the
pollutant could be desorbed using 50% (EtOH/H2O). Although,
earlier, Essandoh et al. [28] had reported a higher q value of
134 mg/g using biochar obtained from the fast pyrolysis of
switchgrass. The polar functional groups present within the
biochar were attributed to the high q value. Some studies have
reported 2,4-D adsorption on date stone-based activated carbon
[31], graphene nano-sheets [32], red-mud [33], activated carbon
composite [33], traditional kiln charcoal [34], biochar from cherry
pits, Jatropha press-cake waste pellets, chopped bamboo pieces,
sugarcane bagasse pellets, pine forestry waste pellets and pecan
shells [35], graphitic carbon nanostructures from filter paper and
cotton [36], granular activated carbon [37], powdered activated
carbon [38], montmorillonite [39], biosorbent from apple shell,
orange peel, banana peel and millet waste [40], activated carbon
from waste orange peel [41], rice straw char from open burning
[42], activated carbon from banana leaves [43], commercial
activated carbons [44] and Fe-crosslinked chitosan complex
[45]. So far, a strong research interest on 2,4-D is observed in
recent times that is beyond any other pesticide or herbicide in use
in contemporary times. This is due to the wider applicability in
farming practice.
Ametryn
Ametryn is a whitish or colorless solid, used to combat
broadleaf and grassy weeds in potato, banana, pineapple, maize,
and sugarcane plantations [46]. Its toxicity to humans includes
vomiting, diarrhea, nausea, salivation, muscle weakness, and
cancer [46]. It also has toxic to both terrestrial and aquatic animals.
Ali et al. [46] studied the sorption of ametryn onto iron
nanoparticles modified with 1-butyl-3-methyl imidazolinium
bromide. The study focused on the modeling of the mass transfer
kinetics and thermodynamics. The results fitted well to the
Langmuir equilibrium isotherm models and best fit the pseudo-
second-order kinetic model. Thermodynamically, the sorption was
exothermic and spontaneous. Elsewhere, Ayranci and Hoda [47]
observed that AC cloth (with a surface area of about 2500 m2/g)
had a monolayer sorption capacity of 354.61 mg/g for ametryn. Suo
et al. [48] used P-doped biochar from a mixture of corn straw, cob,
and starch activated with phosphoric acid for the sorption of
ametryn. Suo et al. [48] ascribed the adsorbate uptake to
electrostatic interactions between the positively charged mole-
cules of ametryn in solution and the biochar's negatively charged
surface.
Amitrole
Amitrole is an odorless and colorless white crystalline powder.
It is a broad non-selective herbicide used to control aquatic grasses
and broadleaf weeds. In humans, amitrole can cause diarrhea, skin
rash, nose bleeding, and vomiting [49]. Aumeier et al. [49]
conducted a preliminary study of the temperature swing adsorp-
tion of amitrole using granular activated carbon via in situ
regeneration. Based on the initial results, the authors suggested
that the process could be used for the mitigation of amitrole water
pollution [49]. Also, Gu et al. [50] studied the sorption of amitrole
onto organo-montmorillonite modified with a zwitterionic sur-
factant (3-[N, N-dimethyl hexadecyl ammonio] propane
123
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
sulfonate). They observed that the sorption was of electrostatic
interactions at the sorptive-sorbent interface.
Atrazine
Atrazine is protonated at the nitrogen of the heterocyclic ring by
a hydrogen ion (in acid medium), making it readily absorbable onto
negatively charged surfaces [51]. It is a non-combustible colorless
solid herbicide used to mitigate against broadleaf and grassy
weeds in sorghum, pineapple, corn, sugarcane plantations, roses,
raspberries, and young woodlands [52]. Atrazine is an endocrine-
disrupting chemical (EDC) that retardates sexual and embryonic
development and variations in pubertal growth in humans and
animals [52]. Ali et al. studied the adsorption isotherm, kinetics,
and thermodynamics of atrazine onto iron nanoparticles modified
with 1-butyl-3-methyl imidazolinium bromide [52]. Their results
fitted well to the Langmuir equilibrium isotherm model, the
pseudo-second-order kinetic model. The adsorption was exother-
mic and spontaneous. Lately, Chen et al. reported a q value of
0.0364 mg/g for atrazine using glutaraldehyde-modified wheat
straw, among other pesticides [53]. Earlier, Coldebella et al.
removed atrazine from water using Moringa oleifera pods, modified
with methanol at 300  C [51]. The qmax value reported was 7.47 mg/
g. Later, Cusioli et al. [54] used a similar thermochemical
modification for Moringa oleifera seed husk, which achieved a
higher qmax of 10.32 mg/g. Many other studies on the adsorption of
atrazine have also been conducted. They include the use of
biosorbents from Moringa oleifera seed husk [55], Chlorella vulgaris
[56], biochars from softwood (Pinus radiata) and hardwood
(Populus euramericana) shavings [57], biosorbent from eucalyptus
(Eucalyptus tereticornis L.) bark [58], activated carbon from Thevetia
peruviana seed [59], molecularly imprinted polystyrene [60],
montmorillonite, sepiolite, illite, palygorskite and muscovite [61],
biochar from the mixture of corn straw, cob and starch [48] and
activated carbon from waste hemp (Cannabis sativa) fibers [62].
Besides 2.4-D, atrazine is the other herbicide with a significantly
high research interest in recent times.
Bentazon
Bentazon is used to control weeds and sedges in farms of corn,
rice, peanuts, peas, and beans [63]. In humans, bentazon leads to
the respiratory tract's irritation, irritation of the skin and eyes,
nausea, vomiting, and breathing difficulty. Shirzad-Siboni et al.
[63] investigated the use of montmorillonite clay modified by
cetyltrimethylammonium bromide (CTAB) for the sorption of
bentazon. The sorption was optimal in acidic medium (pH below
the pHpzc of 4.4) because it is a predominantly anionic weak acid.
However, below pHpzc of 4.4, it possesses a net positive charge,
which favors its sorption onto the modified clay's negatively
charged surface. Bruzzoniti et al. [64] studied the sorption of
bentazon using mesoporous silica. High pH did not favor the
adsorption process because the bentazon becomes present in its
ionized form and repulses the negatively charged adsorbent
surface. This ionic repulsion makes it difficult for the adsorbate to
overcome the mass transfer limitation on the adsorbent's liquid
film boundary. Also, Salman and Khadim [43] investigated the use
of banana leaves-derived activated carbon for bentazon sorption in
a study.
Diquat
Diquat controls broadleaf weeds and grassy weeds in potato,
sugarcane, banana, and vibes farms [65]. In humans, diquat causes
restlessness, irritations of the eye and skin, disorientation, and
failure of the central nervous system [65]. Most recently, Duman
et al. [65] reportedly achieved a monolayer sorption q value of
25.5 mg/g (at 45  C) of diquat from aqueous media using nano-
magnetically modified multi-walled carbon nanotubes (MWCNTs).
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
However, the researchers observed that the MWCNTs not
impregnated by iron nanoparticles had twice the q value for the
specific pollutant. In their discussion, Duman et al. [65] explained
that the two benzene rings on diquat were opined to have
facilitated p–p interaction between the rings and the p-electrons
of the adsorbent. Two years earlier, Vinhal et al. [66] studied
diquat’s sorption onto polyurethane foam. In their approach, the
adsorbate forms an ion associate with counter-ion dodecyl sulfate
(DDS) with polyurethane serving as the solid phase. They
concluded that three DDS units were bound to a diquat molecule,
thereby retaining the adsorbate onto the solid phase effectively.
Diuron
Diuron is a white crystalline solid herbicide used for various
broadleaf, grasses, and weeds [67]. Diuron causes skin and eye
irritation in humans. Al Bahri et al. [67] investigated the use of CO2-
activated granular activated carbon obtained from grape seeds for
the sorption of diuron from aqueous media. The study revealed a q
value of 470 mmol/g. Al Bahri et al. [67] observed that the
multilayer adsorption process was inherently favorable due to the
compound’s low water solubility. The sorption kinetics was
reportedly pseudo-second-order, suggesting that both the number
of active sites and the concentration of pollutant ions in solution
are critical to the diuron uptake rate. In another report, Ayranci and
Hoda [47] observed that activated carbon cloth (surface area of
2500 m2/g) had a monolayer q of 213.06 mg/g for diuron. Of
recent was the work of Bezerra et al. [68] on the sorption of diuron
onto Moringa oleifera seed husk-based biosorbent. They obtained a
qmax of 14.74 mg/g at pH 5 and 45  C. They further explained that its
affinity for organic matter drives diuron adsorption, i.e., the
adsorbent's surface chemistry is responsible for the non-ionic
interactions (such as van der Walls and p–p bonds) that ensue at
the adsorption interphase. Two other recent studies evaluated the
performance of TiO2–reduced graphene oxide nano-adsorbent
[69] and precipitated silica, zeolite, and carbon molecular sieves
[70] for diuron adsorption.
Fenuron
Fenuron is a colorless and nearly-odorless powder herbicide,
commonly used for broadleaf weeds and woody plants in the
cropping of sugar beet, spinach, beans, peas, etc. In humans, it
irritates the respiratory tract, skin, and eyes [71]. Other severe
forms of toxicity include nausea, vomiting, abdominal pains, and
diarrhea [71]. Ali et al. [71] investigated the sorption of fenuron
onto multi-walled carbon nanotubes (MWCNTs). They observed
that liquid film diffusion was the primary adsorption mechanism.
At high pH, fenuron becomes neutral, while the MWCNTs become
negatively charged, favoring the sorption process. The ligands were
collected on the MWCNTs interstitially. The researchers also
discovered that the adsorbent-adsorbate complex was stabilised
by 12 hydrophobic interactions and a single hydrogen bond. The
study was able to establish the suitability of the adsorbent for the
intended purpose.
Glyphosate
Glyphosate is a white crystalline powder used to control
wooden plants, broadleaf weeds, and grasses. Its major toxicology
in humans is skin and eye irritations. However, it can lead to death
on exposure to overdose. Yang et al. [72] studied glyphosate's
sorption onto a metal-organic framework on graphene oxide. They
reported a qmax of 482.7 mg/g. At pH below 4, the glyphosate
uptake was low due to intense competition with hydrogen ions.
However, at pH of 4–5, sorption was considered optimal as the
adsorbent’s Zr
OH groups showed a higher affinity towards the
adsorbate ions than hydrogen ions. Elsewhere, Carneiro et al. [73]
used chitosan/alginate membranes for the sorption of glyphosate
124
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
(achieving a qmax of 10.88 mg/g). Of late, Ramrakhiani et al. [74]
used spent waste activated sludge from heavy metal adsorption for
the same purpose. By evaluating the biosorbent stability, they
observed that desorption only occurred at extreme (high or low)
pH within human regulatory limits. In a similar work, Rivoira et al.
[75] used SBA-15 impregnated with iron nanoparticles. Therein,
they established that in such form, the adsorbent could adequately
remove glyphosate. Further, they showed that 12.5 mM of NaOH
would effectively desorb glyphosate from the SBA-15 matrix and
regenerate it for subsequent reuse.
Isoproturon
Isoproturon is a colorless crystalline solid herbicide. Exposure
to humans can lead to damage to the spleen, liver, kidney, and
testes. Onto activated carbon from guava seeds impregnated with
TiO2, Dávila-Jiménez et al. [76] obtained a q of 10.5 mg/g at 3.3 g/l
isoproturon dosage. The process was a combination of adsorption
and photocatalytic decomposition. Later, Chen et al. [53] utilized
glutaraldehyde-modified wheat straw for isoproturon’s sorption
along with other pesticides. It was observed that the q value of the
adsorbent for isoproturon was about 0.0199 mg/g. Other studies on
isoproturon sorption have evaluated the use of biosorbent from
Chlorella vulgaris [56] and biochar from softwood (Pinus radiate),
and hardwood (Populus euramericana) shavings [57].
Linuron
Linuron is a colorless, odorless, substituted phenyl-urea
crystalline solid compound. It is used in grassy and perennial
broadleaf weeds in soybean, carrot, cotton, potato peas, and fruit
farmlands [77]. To man, it is carcinogenic, forms cell tumors, toxic
to the reproductive system, and capable of inducing liver
dysfunction [78]. Khalfaoui et al. [79] studied linuron's sorption
onto adsorbents prepared from the modified cellulose of Juncus
acatus plant. The fibers were modified using diethylenetriamine
and subsequently loaded with Cu(II) ions. The adsorbent had a q
value of 64.8 mg/g at 20  C and pH 7. The study observed that lower
temperatures favored the pollutant sorption, i.e., it was an
exothermic process. Also, the fibers' modification with Cu(II) ions
increased the adsorbent's affinity to linuron. The results suggest
that linuron is a suitable ligand in the metal coordinating process
[79]. Further investigations by Khalfaoui et al. [79] revealed that
several linuron molecules are adsorbed per site, and the
aggregation phenomenon is catalyzed by the increase of the
receptor sites and higher surface energy. Belaroui et al. [78] studied
the sorption of linuron using palygorskite modified with magnetic
iron. The maximum monolayer sorption capacity was 1.695 mg/g.
The modification enhanced the adsorbent's capability by improv-
ing its surface contact and interactions with palygorskite, an
original, hydrophobic material. For the experiments by Rissouli
et al. [77], the monolayer q values for linuron onto chitin and
chitosan were 5.91 and 21.73 mg/g, respectively. Other similar
studies have reported the use of molecularly imprinted polysty-
rene [60], montmorillonite, sepiolite, illite, palygorskite, and
muscovite [61] for the control of linuron.
MCPA
MCPA (2-methyl-4-chlorophenoxyacetic acid) is a whitish to
light brownish solid herbicide used to control weeds in maize, rice,
wheat, barley, and rye fields [28]. Besides, it is toxic to birds and
aquatic animals. Abdeldaiem et al. [29] studied the sorption of
MCPA onto commercial activated carbon (AC) obtained from
maritime pine wood chemically activated with phosphoric acid
and commercial AC obtained by steam activation of peat, with q
values of 2.60 and 2.08 mmol/g, respectively. The structure of
MCPA possesses both moderately activating and weakly deactivat-
ing functional groups, hence the easy modification of its charge
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
density. The molecule is negatively charged in acidic solution and
would electrostatically adsorb onto positively charged surfaces.
This justifies the suitability of the adsorbents mentioned above for
removing MCPA from aqueous solutions. Essandoh et al. [28]
observed a q value of 50 mg/g of MCPA onto biochar obtained from
the fast pyrolysis of switchgrass. The polar functional groups
present within the biochar were observed to be responsible for the
adsorbate uptake from solution. Kamaraj et al. [32] obtained a
monolayer q value of 411.1 mg/g for the sorption of MCPA onto
graphene nano-sheets. Other studies have evaluated MCPA
adsorption using activated carbon from waste orange peel [41]
and commercial activated carbons [44].
mCPP
Meta-Chlorophenylpiperazine (mCPP) is a solid household
herbicide commonly used against broadleaf weeds. MCPP is a
carcinogen to humans and animals [80]. Kamaraj et al. [80]
prepared zinc hydroxide by electro-synthesis to remove mCPP
from aqueous solution. They developed a large-scale setup for the
process. By achieving 73%–77% removal efficiency, the technology
was surmised as promising for the intended application. In
another work by the group, Kamaraj et al. [32] reported a
monolayer q value of 380.64 mg/g for the sorption of mCPP onto
graphene nano-sheets. A year later, Pandiarajan et al. [41] upped
the q value to 574.71 mg/g using activated carbon from waste
orange peel.
Metribuzin
Metribuzin is a crystalline white solid used as a pre- and post-
emergence herbicide in farms of tomatoes, peas, maize barley, soya
beans, and alfalfa [81]. At low concentrations, Metribuzin does not
pose any health risk. However, at high concentrations, it can cause
the failure of the liver and thyroid glands. Behloul et al. [82] studied
removing metribuzin from polluted water using Pleurotus mutilus
(mycelial basidiomycetes fungus)-based biosorbent. The research-
ers conducted a thorough parametric study of the process. They
reported that at very low pH (pH 2), the negatively charged active
sites are protonated, thereby hindering the sorption of metribuzin.
The optimal pH was 3–4, where adsorption competition was less
prominent. Elsewhere, Essandoh et al. [81] observed qmax values of
223 and 205 mg/g for metribuzin by non-magnetic and magnetic
switchgrass-based biochar, respectively. Before this research,
Kitous et al. [83] modeled metribuzin sorption kinetics onto
electro-activated granular carbon. Their results revealed that
electro-activation of the adsorbent accelerates the sorption
adsorbate by three folds.
Paraquat
Paraquat is a yellowish solid with a faint ammonia-like odor. It
is a non-selective quick-acting herbicide. It is highly toxic in
humans and can lead to the heart, lungs, liver, and kidney failure.
Gu et al. [50] studied the sorption of paraquat onto organo-
montmorillonite modified with a zwitterionic surfactant (3-[N, N-
dimethyl hexadecyl ammonio] propane sulfonate). They reported
that the sorption mechanism was majorly electrostatic interactions
between the negatively charged clay particles and the adsorbate
species. More recently, Jodeh et al. [84] published their work on
removing paraquat using ketoenol–pyrazole functionalized silica
adsorbent, achieving a q value of 17.63 mg/g. The sorption process
was reportedly favored by alkaline pH because there is competitive
adsorption with H+ at lower pH leading. Elsewhere, Vinhal et al.
[85] evaluated the paraquat uptake onto polyurethane foam by the
ion-pairing technique. They claimed that a lack of specific acid-
base groups in the paraquat structure means much of the
interaction with hydrogen ions is with the nitrogen functionalities
on the compound via H-bonding. On this premise, the sorption of
125
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
the paraquat would invariably be favored at higher pH. In the same
year, Zhou et al. [86] functionalized pillararenes with SiO2 for
paraquat sorption. The adsorption kinetics and mechanism were of
the pseudo-first-order kinetic model and the Langmuir isotherm
model, respectively, ascribed to a monolayer adsorption process
that depends majorly on the number of active sites present (and
not necessary on adsorbate concentration in solution).
Other herbicides
Besides the recent advances already mentioned, several others
have been done on other herbicides in recent times. For instance,
2,4,5-T and other chlorophenoxyacetic acid herbicides have been
reportedly used on broadleaf and grassy weeds [87]. The
adsorption was enhanced by combining with simultaneous
photocatalytic degradation. In another report, Phuong et al. [87]
utilized Mg-Fe-Ti layered double hydroxides to adsorb 2,4,5-T.
Kamaraj et al. [32] used graphene nano-sheets to remove 2,4,5-T
from aqueous solution (obtaining a monolayer q of 211.86 mg/g).
Also, Pandiarajan et al. [41] obtained a monolayer q of 416.67 mg/g
for 2,3,5-T using activated carbon from waste orange peel. Also,
Cara et al. [88] studied chlorsulfuron (a sulfonylurea herbicide)
removal from aqueous solution using alkaline treated wheat and
corn straws. The monolayer q value of the wheat and corn straws
were 337.22 and 318.31 mg/g, respectively. The sorption was
observed to be monolayer (Langmuir best-fit), and the kinetics was
pseudo-second-order. However, two kinetic regimes were ob-
served: a rapid regime (lasting 3–4 h) controlled by the adsorbate's
diffusion into the macro-pores and a slower regime (lasting over
6 h).
Okumuş et al. [40] investigated the use of biosorbent from
apple shell, orange peel, banana peel, and millet waste for the
sorption of 2,4-DP, achieving monolayer q values of 25.64, 23.25,
21.27, and 20.83 mg/g, respectively. Likewise, Kamaraj et al. [32]
used graphene nano-sheets to remove 2,4-DP from aqueous
solution but with a much higher q value of 520.83 mg/g. Finally,
Pandiarajan et al. [41] obtained a monolayer q value of 215.52 mg/g
using activated carbon from waste orange peel, whereas developed
Poly(methacrylic acid)/SiO2/Al2O3 by free-radical polymerisation
then sol-gel process for the sorption of imazethapyr from aqueous
solution. Though the latter study focused on the polymer
synthesis, the q value was evaluated as 4.5 mg/g, which was
comparatively higher than for other synthetic polymers used in
imazethapyr adsorption. They summarized their report thus: the
sorption process is more favorable in the acid medium as the
adsorbate is protonated to a neutral form which promotes the
hydrogen bond interaction with the functional groups of the
polymer adsorbent [89].
Table 3 gives a comprehensive list of the q values of various
adsorbents used for herbicides removal from aqueous solutions
reported in open literature in recent times (reported to four
significant figures). Also, pH and temperature are often kept
constant when determining the monolayer adsorption capacity
[90,91]. We also state the major mechanism of adsorbate uptake, as
reported in the articles.
Pesticides
Aldrin
Aldrin is a colorless, chlorinated cyclo-diene solid. High
exposure to aldrin is carcinogenic and can also lead to immune,
endocrine, nervous, and cardiovascular systems dysfunctionalities
[109]. Bakka et al. [109] studied the sorption of aldrin by
biosorbents prepared from aqueous solution by treated patellidae
shells. They obtained a qmax of 208.33 mg/g. The sorption process
was noticeably exothermic. The researchers also inferred that Van
der Waals and dipole forces play essential roles in the biosorption
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 3
Summary of sorption capacities (q) of various adsorbents for herbicides.

S/N Herbicide Adsorbent Conditions q (mg/g or Major uptake mechanism Ref.

mmol/g+)
1 2,4,5-T AC from waste orange peel T = 303 K, pH 3 416.7 Physisorption [41]
Graphene nano-sheets T = 303 K, pH 3 211.9 Physisorption [32]
Mg–Fe–Ti layered double hydroxides – – – [87]
2 2,4-D Modified bentonite T = 298 K, pH 3
8 50.36 Physisorption [27]
Montmorillonite T = 318 K, pH 2 1067 Physisorption [39]
Biochar from various biomass – – – [35]
Commercial AC T = 298 K, pH 2 3.690+ Electrostatic interaction [92]
Commercial AC (GAB) T not stated, pH 3
8 367.2 Electrostatic interaction [44]
Commercial AC (CPB) T not stated, pH 3
8 273.1 Electrostatic interaction [44]
AC from waste orange peel T = 303 K, pH 3 515.5 Physisorption [41]
Fe-crosslinked chitosan T = 303 K, pH 5 473.0 Electrostatic and [45]
p–p interaction
Biochar from switchgrass T = 308 K, pH 2 134.0 H-bonding [28]
Graphene nano-sheets T = 303 K, pH 3 295.9 Physisorption [32]
AC from banana leaves – – – [43]
Red-mud–AC composite T = 298 K, pH 3 111.1 – [33]
Powdered AC T = 298 K, pH not stated 90.40 – [38]
Traditional kiln charcoal – – – [34]
AC from pine wood activated with T = 298 K, pH 3
5 1.560+ p–p interactions [29]
phosphoric acid
AC from steam activation of peat T = 298 K, pH 3
5 1.490+ p–p interactions [29]
Biosorbent from apple shell T not stated, pH 6 17.86 – [40]
Biosorbent from orange peel T not stated, pH 6 34.48 – [40]
Biosorbent from banana peel T not stated, pH 7 22.73 – [40]
Biosorbent from millet waste T not stated, pH 7 29.40 – [40]
Graphitic nanocarbon from filter paper T = 303 K, pH 2 77.00 – [36]
Graphitic nanocarbon from cotton T = 303 K, pH 2 33.00 – [36]
Chitosan–MOF composite T = 298 K, pH 3 892.9 H-bonds [93]
Rice straw char from open burning – – p–p interactions [42]
AC from date stones T = 303 K, pH 2 238.1 Pore diffusion [31]
3 2,4-DB Biosorbent from apple shell T not stated, pH 6 40.08 – [40]
Biosorbent from orange peel T not stated, pH 6 22.71 – [40]
Biosorbent from banana peel T not stated, pH 7 33.26 – [40]
Biosorbent from millet waste T not stated, pH 7 45.45 – [40]
4 2,4-DP AC from waste orange peel T = 303 K, pH 3 215.5 Physisorption [41]
Graphene nano-sheets T = 303 K, pH 3 520.8 Physisorption [32]
Biosorbent from apple shell T not stated, pH 6 25.64 – [40]
Biosorbent from orange peel T not stated, pH 6 23.25 – [40]
Biosorbent from banana peel T not stated, pH 7 21.27 – [40]
Biosorbent from millet waste T not stated, pH 7 20.83 – [40]
5 Acetochlor Modified montmorillonite – – – [94]
Modified bentonite – – Chemisorption [95]
6 Alachlor TiO2–reduced graphene oxide – – – [69]
Montmorillonite, sepiolite, illite, – – – [61]
palygorskite and muscovite
7 Ametryn Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
Modified iron nanoparticles T = 293 K, pH 7 0.014 Liquid film diffsuion [46]
Activated carbon cloth T = 298 K, pH not stated 354.6 – [47]
8 Amitrole Granular AC – – – [49]
Modified montmorillonite – – Electrostatic attraction [50]
9 Atraton Molecularly imprinted polystyrene T = 298 K, pH not stated 1.705 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 1.612 – [60]
10 Atrazine Corks of Quercus spp. trees – – – [96]
Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.036 – [53]
Thermo-chemically modified Moringa T = 318 K, pH 5 10.32 Electrostatic attraction [54]
oleifera seed husk
Functionalized MWCNTs T = 298 K, pH not stated – p–p interaction [97]
Biosorbent from Moringa oleifera seed husk – – – [55]
Biosorbent from Chlorella vulgaris – – – [56]
AC from Thevetia peruviana seed T = 203 K, pH 6 9.270 – [59]
Thermo-chemically modified Moringa T = 298 K, pH 5 7.470 Electrostatic attraction [51]
oleifera pods and H-bonds
Biochars from wood shavings – – – [57]
Chemically modified iron nanoparticles T = 293 K, pH 7 0.012 Liquid film diffusion [52]
Molecularly imprinted polystyrene T = 298 K, pH not stated 3.794 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 0.826 – [60]
AC from waste hemp fibers T = 298 K, pH not stated 14.50 p–p interaction [62]
Biosorbent from eucalyptus (Eucalyptus T = 298 K, pH not stated 936.1 – [58]
tereticornis L.) bark
Polyaniline derived carbon T = 298 K, pH 7 943.0 Van der Waal's forces [98]
Granular AC T = 298 K, pH 7 123.0 Van der Waal’s forces [98]

126
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 3 (Continued)
S/N Herbicide Adsorbent Conditions q (mg/g or Major uptake mechanism Ref.
mmol/g+)
Montmorillonite, sepiolite, illite, – – – [61]
palygorskite and muscovite
11 Atrazine- desisopropyl Molecularly imprinted polystyrene T = 298 K, pH not stated 1.351 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 6.870 – [60]
12 Bentazon AC from banana leaves – – – [43]
Mesoporous silica – – – [64]
Montmorillonite modified by CTAB T = 298 K, pH 3 500.0 – [63]
13 Carbetamide Hydrotalcite and organohydrotalcites – – – [99]
14 Carbofuran AC from banana leaves – – – [43]
Biosorbent from Chlorella vulgaris – – – [56]
15 Chlorotriazine Unmodified kaolinite T = 303 K, pH 12 142.9 – [100]
Acid modified kaolinite T = 303 K, pH 8 83.33 – [100]
Alkali modified kaolinite T = 303 K, pH 9 90.90 – [100]
16 Chlorsulfuron Alkaline treated wheat straws T = 298 K, pH Not stated 337.2 Multiple [88]
Alkaline treated corn straws T = 298 K, pH Not stated 318.3 Multiple [88]
17 Chlortoluron Diatomite T = 298 K, pH 5 1000 – [101]
18 Cyprazine TiO2–reduced graphene oxide – – – [69]
19 Desmetryn Functionalized MWCNTs T = 298 K, pH not stated 285.0 p–p interaction [97]
20 Dicamba Intercalated double hydroxide T = 298 K, pH 2 279.0 Electrostatic interactions [102]
AC from Laponite with cassava starch T = 298 K, pH 7 251.9 Chemisorption [103]
21 Difenzoquat Polyurethane foam – – Pore diffusion [66]
22 Dimethoate Biosorbent from Chlorella vulgaris – – – [56]
23 Dinoseb Activated carbon cloth T = 298 K, pH Not stated 301.8 – [47]
24 Diquat Nano-magnetic oxidised MWCNTs T = 298 K, pH 6.5 25.50 Electrostatic and [65]
p–p interaction
Oxidesed MWCNTs T = 298 K, pH 6.5 74.00 Electrostatic and [65]
p–p interaction
Polyurethane foam – – Pore diffusion [66]
25 Diuron Biosorbent from Moringa oleifera seed T = 318 K, pH 5 14.74 Physisorption [68]
husks
TiO2–reduced graphene oxide – – – [69]
Precipitated silica, zeolite and carbon – – – [70]
molecular sieves
Polyaniline derived carbon T = 298 K, pH 7 884.0 H-bonds [98]
Granular AC T = 298 K, pH 7 78.00 H-bonds [98]
Granular AC from grape seeds T = 318 K, pH 6.1 0.470 Pore diffusion [67]
Activated carbon cloth T = 298 K, pH not stated 213.1 – [47]
26 Fenuron MWCNTs – – – [71]
27 Glyphosate Spent waste activated sludge from heavy T = 293 K, pH 5
6 6.034 Multiple [74]
metal adsorption
MOF on graphene oxide T = 298 K, pH 4 482.7 Chemisorption [72]
SBA-15 with iron nanoparticles – – Complexation [75]
Chitosan/alginate membranes T = 298 K, pH 6.5 10.88 – [73]
28 Imazapic Biochar from empty fruit bunch (300  C) T = 298 K, pH 6
7 19.65 Chemisorption [104]
Biochar from rice husk (300  C) T = 298 K, pH 6
7 17.52 Chemisorption [104]
Chitosan modified EFB biochar T = 298 K, pH 5.56 19.96 – [105]
EFB biochar T = 298 K, pH 6.41 16.35 – [105]
Chitosan modified rice husk biochar T = 298 K, pH 7.13 17.94 – [105]
Rice husk biochar T = 298 K, pH 6.00 13.15 – [105]
29 Imazapyr Biochar from empty fruit bunch (300  C) T = 298 K, pH 6
7 24.52 Chemisorption [104]
Biochar from rice husk (300  C) T = 298 K, pH 6
7 20.89 Chemisorption [104]
Chitosan modified EFB biochar T = 298 K, pH 5.99 25.95 – [105]
EFB biochar T = 298 K, pH 6.35 20.56 – [105]
Chitosan modified rice husk biochar T = 298 K, pH 7.09 21.07 – [105]
Rice husk biochar T = 298 K, pH 5.97 16.98 – [105]
30 Imazethapyr Poly(methacrylic acid)/SiO2/Al2O3 T = 343 K, pH 2 4.470 Pore diffusion [89]
31 Isoproturon Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.019 – [53]
Diatomite T = 298 K, pH 5 250.0 – [101]
Biosorbent from Chlorella vulgaris – – – [56]
AC from guava seeds impregnated with TiO2 T = 293 K, pH 6 10.50 – [76]
Biochars from wood shavings – – – [57]
32 Linuron Palygorskite modified with iron T = 293 K, pH not stated 1.695 – [78]
Chitin T = 298 K, pH 5 5.910 – [77]
Chitosan T = 298 K, pH7 21.73 – [77]
Molecularly imprinted polystyrene T = 298 K, pH not stated 1.918 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 2.105 – [60]
Juncus acatus cellulose fibers T = 293 K, pH 7 64.80 – [79]
Montmorillonite, sepiolite, illite, – – – [61]
palygorskite and muscovite
33 MCPA AC from waste orange peel T = 303 K, pH 3 414.9 Physisorption [41]
Commercial AC (CPB) T not stated, pH 3
8 399.9 Electrostatic interaction [44]
Commercial AC (GAB) T not stated, pH 3
8 599.9 Electrostatic interaction [44]
Biochar from switchgrass T = 308 K, pH 2 50.00 H-bonding [28]
Graphene nano-sheets T = 303 K, pH 3 411.1 Physisorption [32]
AC from pine wood activated with T = 298 K, pH 3
5 2.600+ p–p interactions [29]
phosphoric acid

127
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 3 (Continued)
S/N Herbicide Adsorbent Conditions q (mg/g or Major uptake mechanism Ref.
mmol/g+)
AC from steam activation of peat T = 298 K, pH 3
5 2.080+ p–p interactions [29]
34 MCPP Zinc hydroxide 793.7 [32]
AC from waste orange peel T = 303 K, pH 3 574.7 Physisorption [41]
Graphene nano-sheets T = 303 K, pH 3 380.6 Physisorption [32]
35 Metamitron Hydrotalcite and organohydrotalcites – – – [99]
36 Metolachlor Biosorbent from Chlorella vulgaris – – – [56]
Biochars from wood shavings – – – [57]
37 Metribuzin Biosorbent from Pleurotus mutilus fungus – – – [82]
Biochar from switchgrass T = 308 K, pH 2 223.0 H-bonds [81]
Magnetically modified biochar from T = 308 K, pH 2 205.0 H-bonds [81]
switchgrass
Electro-activated granular carbon – – – [83]
38 Molinate Biosorbent from Chlorella vulgaris – – – [56]
39 Nicosulfuron Polyaniline/BEA zeolite composites T = 296 K, pH 5 29.80 H-bonds [106]
40 Pendimethalin Biosorbent from Chlorella vulgaris – – – [56]
Paraquat Functionalised silica T = 298 K, pH 11 17.63 Physisorption [84]
Modified montmorillonite – – Electrostatic attraction [50]
Polyurethane foam – – Film and Pore diffusion [85]
Pillararenes functionalised with SiO2 – – – [86]
41 Penconazole Montmorillonite, sepiolite, illite, – – – [61]
palygorskite and muscovite
42 Prometon Rice straw char from open burning – – p–p interactions [42]
43 Prometryn Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.038 – [53]
Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
Functionalized MWCNTs T = 298 K, pH not stated – p–p interaction [97]
44 Propanil Biosorbent from Chlorella vulgaris – – – [56]
Rice straw char from open burning – – p–p interactions [42]
45 Propazine Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
46 Pyriproxin Biosorbent from Chlorella vulgaris – – – [56]
Sebuthylazine Functionalized MWCNTs T = 298 K, pH not stated – p–p interaction [97]
47 Secbumeton Chemically modified iron nanoparticles T = 293 K, pH 7 0.011 Co-ordination bonding [107]
48 Simazine Biochar from various biomass – – – [35]
Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
Biosorbent from Chlorella vulgaris – – – [56]
49 Simetryne Biochar from a mixture of corn straw, cob, – – Multiple [48]
and starch
50 Terbumeton Functionalized MWCNTs T = 298 K, pH not stated – p–p interaction [97]
51 Tebuthiuron Poly(methacrylic acid–trimethylolpropane T = 298 K, pH 6 186.8 Film diffusion [108]
trimethacrylate)
Poly(vinylimidazole–trimethylolpropane T = 298 K, pH 6 213.9 Film diffusion [108]
trimethacrylate)
52 Terbutryn Functionalized MWCNTs T = 298 K, pH not stated 304.0 p–p interaction [97]

process. Higher temperatures favor the adsorbate’s desorption out Deltamethrin

of the active sites due to increased oscillation energy (hence, a
lesser sorption capacity). Bakka et al. [109] further buttressed the
usefulness of the developed biosorbent by a regeneration test,
which showed that the biosorbent could be reused 5 times with
less than 20% drop in q values.
Carbaryl
Carbaryl is a carbamate-based insecticide used to control
moths, beetles, and other forms of crop-damaging insects [110].
Carbaryl is a negatively charged molecule and would exhibit
electrostatic repulsion with the negatively charged biosorbent
surface at alkaline pH. In aqueous media, carbaryl reacts with
nitrites to form compounds with high mutagenic effects on
humans, even at trace concentrations. Further, Bakka et al. [110]
reported carbaryl adsorption from aqueous solution using
biosorbent prepared from eggshells. A monolayer qmax of
13.18 mg/g was achieved. They also observed that at pHpzc below
8.8, the adsorbent surface becomes positively charged, which
favors removing the pollutant via charge-charge attractions.
Like most other pesticides, deltamethrin is an evasive (colorless
and odorless) solid with a specific gravity of 1.5. Al-Qodah et al.
[111] studied removing deltamethrin from aqueous solution using
oil shale ash modified by 2 M hydrochloric acid. They obtained a
qmax of 10.6 mg/g at 25  C and pH 7.3. In detail, the authors carried
out parametric, equilibrium, and kinetic studies that were
conducted to elucidate other aspects of the surface process. In
other work, Ayranci and Hoda [47] observed that activated carbon
cloth had a monolayer q value of 301.84 mg/g for the adsorptive. A
decade later, Da Fonseca et al. [108] investigated the use of
synthetic polymers poly (methacrylic acid–trimethylolpropane
trimethacrylate) and poly (vinyl imidazole–trimethylolpropane
trimethacrylate) for the removal of tebuthiuron from aqueous
solution with obtained qmax of 186.76 and 213.89 mg/g, respective-
ly. The pesticide interacts with the monomeric unit of the
adsorbent (methacrylic acid and 1-vinyl imidazole) by hydrogen
bonding or London dispersion forces. These interactions are
possible because tebuthiuron is a weak base and would exist in
its molecular form at pH above 2.

128
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
Diazinon
Diazinon is a colorless to dark brownish liquid with a faint ester-
like odor and a specific gravity of 1.116. It is one of the most
commonly used organophosphorus pesticides in agriculture [112].
It is toxic to the ecosystem. In humans, it can lead to nervous
disorder, neuropathy, neurological complications, and even coma
[112]. Heydari et al. [113] applied the Plackett–Burman experi-
mental design on response surface methodology for statistical
optimization of diazinon sorption onto magnetically modified
bentonite clay. Besides determining the optimum level of each
factor, the study determined the monolayer q value as 277.78 mg/g.
Further, the research group investigated the use of multiwall
carbon nanotubes (MWCNTs) for diazinon sorption, and they
observed that the sorption was better in acidic medium. Such
occurrence was due to the hydroxyl group's interactions on the
adsorbent and the protonated nitrogen on the diazinon pyrimidyl
group. Earlier, Moussavi et al. [114] had studied diazinon uptake
onto NH4Cl-induced activated carbon with a qmax of 250 mg/g
reported. In addition to that, they reported the optimum sorption
between pH of 6 and 7. In this case, below pHpzc of 6.6, the
adsorbate becomes negatively charge, leading to the electrostatic
repulsion of negatively charge diazinon molecules. However, above
the pHpzc, the anionic diazinon interacts favorably with the
adsorbate to ensure higher adsorbate uptake. Some other diazinon
studies evaluated the removal efficiency of Fe-doped TiO2
deposited on bentonite [115] and pre-treated alimentary industrial
waste [116] as novel adsorbent.
Imidacloprid
Imidacloprid is a colorless crystalline solid pesticide with a
melting point of 136.4  C and a solubility in water at 20  C of 0.51 g/
l. It is an insecticide used against beetles, bugs, locusts, and
termites. At high concentrations in humans, it leads to disorienta-
tion and drowsiness. Cobas et al. [117] observed a qmax of 8.507 mg/
g for imidacloprid onto biosorbents prepared from chestnut shells.
Two years on, Kalhor et al. [118] studied the sorption of
imidacloprid onto an amine-functionalized silica nano-hollow
spheres. However, not sufficient discussions were presented on the
sorption mechanism as the authors focused on parametric and
kinetic investigations. In another report, Mandal and Singh [58]
carried out imidacloprid sorption on biosorbent prepared from
eucalyptus (Eucalyptus tereticornis L.) bark. The study focused on
fitting experimental data into a wide variety of isotherms, with
detailed error analysis of each model. The monolayer adsorption
capacity from the Langmuir isotherm in the study was 387.1 mg/g.
Based on their results, the biosorbent is considered excellent for
imidacloprid treatment. Other recent studies on the uptake of
imidacloprid from aqueous solution have evaluated the use of
TiO2–reduced graphene oxide nano-adsorbent [69] and magnetic
graphene oxidecyclodextrin composite adsorbent [119] with
varying degrees of success.
Oxamyl
Oxamyl is a colorless crystalline solid, having a melting point of
100
102  C, but changes to a dimorphic form at 108
110  C. It has
a sulphurous odor [120]. Oxamyl is an insecticide (nematicide)
used in controlling nematodes infestation of farms [121]. The
ecotoxicology of oxamyl is well understood; it causes genomic DNA
damage in fishes and humans, leading to nausea, abdominal pain,
excessive sweating, osteoporosis, and miosis with unclear vision
[121]. It inhibits the acetylcholinesterase (part of the human
biological cycle) by the rapid carbamylation of its active site [121].
Agarwal et al. [121] investigated the use of graphene quantum
dots nano-adsorbent in removing oxamyl from aqueous solution
with a qmax of 125 mg/g. The type and ionic state of the functional
groups present on the adsorbents and compound speciation in
129
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
solution affect the adsorption's nature, as the process's pH
dependence intensifies. Agarwal et al. [121] observed an optimum
pH of 8 for the sorption of oxamyl onto graphene quantum dots
nano-adsorbent. Mohammad et al. [120] compared activated
carbon from pomegranate peels, activated carbon from banana
peels, and commercial activated carbon for the sorption of oxamyl
from aqueous solution. The study emphasized the positive
functionality of both biomaterials for the mitigation of oxamyl
pollution based on their comparative performance with commer-
cial activated carbon. Elsewhere, Mohammad and Ahmed [122]
utilized activated carbon from silkworm feces for the same
purpose, achieving a q value of 625 mg/g.
Interestingly, there was no effect of pH change on the
adsorption. Mohammad and Ahmed [122] went further to
elucidate the interactions between oxamyl and the adsorbent.
They claimed the interactions are due to the dispersion forces and
polarisation of p-electrons. This phenomenon is feasible through
the ionization of the nitrogen atom on the compound, resulting in
polar interactions with the chemical groups on the adsorbate.
Triadimenol
Triadimenol is an odorless powder off-white in color. Al-
Shawabkah et al. [123] studied the removal of traidimenol from
aqueous solution using adsorbents prepared from whey sludge.
The authors explained that the process is favored at lower
temperatures. In their report, the solution's viscosity decreases
with increasing temperature, enhancing intra-particle diffusion of
the triadimenol molecules into the active sites. At high tempera-
ture, the weakened adsorbate–adsorbate molecules interactions
were altered, resulting in easy desorption of the adsorbate. In an
acid medium, the amino group on the adsorbate is protonated,
rendering it positively charged. Such occurrence increases the
electrostatic interaction with the activated whey sludge, thereby
increasing the q value. The study by Al-Shawabkah et al. [123]
justified the efficiency of activated whey sludge for the remedia-
tion of triadimenol.
Secbumeton
Secbumeton is an herbicide widely utilized in the control of
weed. The human bio-magnification on secbumeton can lead to
various negative toxicological responses such as skin dryness or
cracking, corneal clouding, dizziness, gastric, and intestinal
problems, drowsiness, etc. [107]. The herbicide is also toxic to
organisms like bacterial and fish algae. Ali et al. [107] studied the
adsorption of secbumeton onto iron nanoparticles modified with
1-butyl-3-methyl imidazolinium bromide. The authors optimized
the adsorption parameters while investigating the kinetics and
thermodynamics of the process. Their results fitted well to the
Langmuir equilibrium isotherm model, pseudo-second-order
kinetic model, and were of exothermic and spontaneous nature.
Table 4 gives a comprehensive list of the q values of various
adsorbents for pesticide removal from aqueous solutions reported
in recent times (written to four significant figures). The pH and
temperature conditions are also reported as these are usually kept
constant when determining the monolayer adsorption capacity
[90,91]. The primary adsorption mechanism is also stated.
Mechanism of H & P adsorption
The mechanism of H & P removal varies for each adsorbate-
adsorbent system, as shown in Tables 3 and 4. For studies where a
proper mechanistic investigation was not reported in line with the
adsorption capacity, these were left as unstated. It will be erratic to
judge from the isotherm modeling and kinetics findings alone. The
pseudo-second-order kinetic model, as best-fit, is not conclusive
proof of the chemisorption mechanism [90,138]. The pseudo-
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 4
Summary of sorption capacities (q values) of various adsorbents for pesticides.

S/N Pesticide Adsorbent Conditions q (mg/g or Major uptake mechanism Ref.

mmol/g+)
1 2-CPA Commercial AC T = 298 K, pH 2 2.250+ Electrostatic interaction [92]
2 3-BrPP Commercial AC T = 298 K, pH 2 2.440+ Electrostatic interaction [92]
Commercial AC – – –
3 4-BrPP Commercial AC T = 298 K, pH 2 2.100+ Electrostatic interaction [92]
4 4-CPA Commercial AC T = 298 K, pH 2 3.340+ Electrostatic interaction [92]
AC with gradually removed external T = 298 K, pH not stated 2.260+ Electrostatic and p–p interaction [124]
particle layers
Commercial AC – – – [125]
Commercial AC T = 298 K, pH 2 2.020+ Electrostatic interaction [92]
5 4-FPP Commercial AC T = 298 K, pH 2 2.040+ Electrostatic interaction [92]
6 8-Quinoline-carboxylic acid Sodium activated montmorillonite T = 298 K, pH 2 65.40 – [126]
Strong acid-activated montmorillonite T = 298 K, pH 2 67.60 – [126]
Organic acid-activated montmorillonite T = 298 K, pH 2 75.90 – [126]
7 Aldicarb Activated carbon cloth T = 298 K, pH not stated 421.6 – [47]
8 Aldrin Acid treated patellidae shells T = 295 K, pH 4 208.3 Physisorption [109]
9 Acetamiprid Graphene oxide–cyclodextrin composite – – – [119]
Biosorbent from chestnut shells T = 298 K, pH not stated 4.698 – [117]
AC from waste hemp fibers T = 298 K, pH not stated 19.30 p–p interactions [62]
10 Bensulfuron-methyl Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.029 – [53]
11 Bromopropylate AC from corn cob T = 295 K, pH not stated 0.189 – [127]
AC from olive kernel T = 295 K, pH not stated 0.123 – [127]
AC from soya stalks T = 295 K, pH not stated 0.116 – [127]
AC from rapeseed stalks T = 295 K, pH not stated 0.079 – [127]
12 Carbaryl Biosorbent from eggshells T = 295 K, pH 4 13.18 Physisorption [110]
13 Carbofuran AC from waste hemp fibers T = 298 K, pH not stated 13.00 p–p interactions [62]
14 Carboxin Molecularly imprinted polystyrene T = 298 K, pH not stated 3.188 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 1.351 – [60]
15 CFA AC with gradually removed external T = 298 K, pH not stated 2.060+ Electrostatic and p–p interaction [124]
particle layers
16 Chlorpyrifos Corks of Quercus cerris and Quercus suber – – – [96]
trees
Nanocellulose T = 308 K, pH 7.4 7.240 Multiple [128]
Molecularly imprinted polystyrene T = 298 K, pH not stated 11.10 – [60]
Non-imprinted polystyrene T = 298 K, pH not stated 17.95 – [60]
17 Clothianidin Graphene oxide–cyclodextrin composite – – – [119]
18 Deltamethrin Acid treated oil shale ash T = 298 K, pH 7.3 10.96 – [111]
19 Diazinon Modified bentonite T = 298 K, pH 4.5 27.03 – [115]
MWCNTs – – – [112]
Magnetically modified bentonite T = 298 K, pH 2 277.8 Physisorption [113]
Alimentary industrial waste T = 288 K, pH 7.3 18.52 Electrostatic interaction [116]
NH4Cl-induced AC T = 288 K, pH 7 250.0 Electrostatic interaction [114]
20 Dimethoate AC from waste hemp fibers T = 298 K, pH not stated 14.70 p–p interactions [62]
21 Heptachlor Biosorbent from pine bark – – – [129]
Modified bentonite T = 318 K, pH 7.5 0.188 – [130]
22 Imidacloprid Silica nano hollow sphere – – – [118]
Graphene oxide–cyclodextrin composite – – – [119]
Biosorbent from chestnut shells T = 298 K, pH not stated 8.507 – [117]
Biosorbent from eucalyptus (Eucalyptus T = 298 K, pH not stated 387.1 – [58]
tereticornis L.) bark
23 Lambda-cyhalothrin Corks of Quercus cerris and Quercus suber – – – [96]
trees
24 Lindane (HCH) Biosorbent from pine bark – – – [129]
AC from coconut shells 650.0 [131]
25 Malathion Biochar from jute fibers T = 301 K, pH 6.57 71.63 Film diffusion [132]
26 Mefenacet Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.043 – [53]
27 Metalaxyl Montmorillonite, sepiolite, illite, – – – [61]
palygorskite and muscovite
28 Methoxychlor Zeolite modified by CTAB – – – [133]
29 Methyl parathion Typha Australis leaf powder T = 298 K, pH 6.8 7.280 Chemisorption [134]
Biosorbent from watermelon peel T = 333 K, pH 6 0.024+ – [135]
30 Nicosulfuron AC from waste hemp fibers T = 298 K, pH not stated 11.60 p–p interactions [62]
31 Nitenpyram Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.025 – [53]
Graphene oxide–cyclodextrin composite – – – [119]
32 Oxamyl AC from silkworm feces T = 298 K, pH 2
10 625.0 Physisoprtion [122]
Graphene quantum dots T =313 K, pH 8 125.0 Electrostatic interaction [121]
AC from pomegranate peels – – – [120]
AC from banana peels – – – [120]
Commercial AC – – – [120]
33 Penoxsulam Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.079 – [53]
34 Pentachlorophenol Bio-char from reeds – – – [136]
35 Pirimicarb Biosorbent from chestnut shells T = 298 K, pH not stated – – [117]
36 Prochloraz Glutaraldehyde modified wheat straw T = 298 K, pH 4.5 0.062 – [53]
37 Profenofos Fe/Ni bimetallic nanoparticles T = 298 K, pH 7 0.202 – [137]

130
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
second model mathematically over-fits adsorption data [138] even
for known physisorption processes. Hence, thermodynamics
studies, desorption studies, and spectroscopic analysis are also
required to properly understand the mechanism. Thus, we used
this whole body of research reports to synthesize our discussion on
the H & P adsorption mechanism.
The controlling mechanism is usually the slowest step of the H
& P adsorption process. The steps are bulk diffusion (i), liquid film
diffusion (ii), intra-particle or pore diffusion (iii), and surface
adsorption (chemisorption or physisorption) (iv). The first step is
rarely a limiting step for the process. Kinetics modeling can be used
to differentiate between liquid film diffusion and intra-particle, or
between pore diffusion and surface adsorption. However, to
determine the specific type and nature of surface adsorption and
the chemical forces involved, a more detailed analysis of
adsorption data is needed.
Usually, chemisorption is controlled by the solution chemistry
and the nature of the adsorbent. The solution chemistry’s essential
parameters are pH and adsorbate pKa, while that of the adsorbent
is the pHzc. At pKa < pH, the adsorbate exists in its molecular form
in solution. In this regime, the uptake mechanism would likely be
due to p–p (dispersive) interactions and H-bonds. However, at
pKa > pH, the adsorbate is protonated and exists in its ionic form.
Depending on the adsorbate ionic charge and the adsorbent's net
surface charge (determined by the pHzc), the interaction could be
electrostatic (acceptor–donor) attraction. Physisorption is by van
der Waal’s forces, and the electronic property of the adsorbate is
unchanged after uptake.
Despite the presence of a dominant mechanism, other
mechanisms can also simultaneously occur in the adsorption
system. The adsorptive process is seldom purely chemical or
physical in nature but some combination of both. These multiple
physicochemical mechanisms include the formation of local
positively charged sites, the p–p dispersion, donor–acceptor
electrostatic interaction, repulsive electrostatic interaction, facile
access of symmetrical solute molecules into adsorbent micropores,
the formation of hydrogen bonds with neighboring solutes or
adsorbent oxygen group [92], van der Waal’s forces and dipole–
dipole forces [28].
Performance evaluation: effect of sorbate-sorbent interphase
The adsorbate solubility and adsorbent surface area have a
significant effect on the extent of sorbate-sorbent interactions. As
part of the systematic review, the solubility, adsorbent surface
area, and adsorption capacity were tabulated and provided in the
Supplementary material. Of the pool of literature evaluated (112
papers in total), we analyzed only 65 reports that provided the
specific surface area (SBET) of the adsorbent used for performance
evaluation. Therefore, the influence of adsorbate’s physical
properties and the sorbents on the preferential separation of the
pollutants are perused.
The new adsorption attributes calculated for the performance
evaluations are the effective surface area (eSBET) (i.e., the portion of
the SBET occupied by the sorbate molecules) and the adsorbate
preferential adsorption, qp (i.e., the ratio of the amount of sorbate
on the sorbent to the amount in solution), and estimated
preferential adsorption. The derivation of eSBET is relevant because
chemical species adsorption depends on the number of relevant
active sites with an adequate affinity for the sorptive, irrespective
of the total SBET of the adsorbent. Since most of the papers reviewed
in the current work did not provide information about the types or
amount of the chemical functionalities on the sorbents, the
derivation of eSBET inform on the relevance of the active sites to the
q, and more importantly, qp value. Thus, the eSBET is expected to
increase linearly with the availability of the relevant chemical
131
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
surface functionality tethered on the SBET, either naturally or
engineered by chemical impregnation [139,140]. Table 5 is a list of
the extracted and calculated adsorption properties and attributes
from the reviewed literature. The Supplementary material
provides detailed information on the calculations made and other
important parameters.
The key index for evaluating the extent of sorbate-sorbent
interphase is the mass adsorption capacity (q, mg/g) of the
adsorbent for a specific pesticide or herbicide. From Table 5, only
19 out of the 66 studies had qp > 1, indicating that the sorbates had
a relatively higher preference for the sorbent than to remain in
solution. Of the 19 cases, four (SN = 15,50,53,54) were 2>qp>1,
seven (SN = 2,33–36,44,59) were 10 > qp > 2, and eight
(SN = 30,32,47–49,52,63,64) evinced qp values between 10 and
50. The highest values were reported by Yavari et al. [104] (SN = 45;
qp = 45) and Mandal and Singh [58] (SN = 30; qp = 40) where
eucalyptus-based biosorbent on atrazine and biochar on imazapic
herbicides were reported, respectively. We further observed that
the q values correlated more strongly with eSBET (+0.3844) than the
conventionally reported SBET (+0.2624). This observation confirms
that other adsorption properties of the adsorbent of surface
chemical nature influence the collection of the target pollutants.
For more specific examination, a chart was plotted showing the
trend in the reported (q and SBET) and derived (qp and eSBET)
adsorption properties for the most researched pollutant (2,4-D in
Fig. 4a) and adsorbent (activated carbon in Fig. 4b). Note that these
plots were designed solely to show the trend among the adsorption
properties and not to compare the researchers' results. Yet, we
noticed that the influence of SBET and q depend largely on the
adsorption conditions as the nature of the sorbent-surface
interface.
The correlation data from the broad dataset and the most
prominent adsorbate (2,4-D) and some commonly used adsorb-
ents (clay, biochar, and AC) are provided in Table 6. Upon the
investigation of individualized analyses, we observed that the
correlations rose significantly, especially for 2,4-D, clay, and AC. By
eyeballing, we noticed that the q showed a similar trend with eSBET
(36.20%) than with SBET (15.63%) when AC was the adsorbent. Yet,
with biochar and 2,4-D (as adsorbent and adsorbate, respectively),
a much superior correlation of the eSBET (over those with SBET) with
q was obvious (Table 6). The negative albeit, mild correlations
observed for all, 2,4-D, clay, biochar, and AC SBET–eSBET pairs
(Table 6) confirm that a high SBET does not necessarily connote an
adsorbent will exhibit high adsorption capacity.
Overall, the derived adsorption properties (qp and eSBET) are
significantly more reliable properties for achieving bias-free
comparison amongst researches with different experimental
conditions and targets such as this review.
An identifiable positive relationship exists between the
preferential adsorption (qp) of the adsorbate over solubility and
the moles of the sorbent. Thus, the higher the sorbent mass in the
solution, the more the adsorbate's mass transfer onto the
adsorbent. As shown in Table 6, the relation between the moles
of sorbent and qp is all positive for all cases (55.5%), and strongly
significant for clay (97%), AC (61.5%), and the focus adsorbate, 2,4-D
(46.9%), indicating the agreement between the adsorptive and the
sorbents in this adsorption relationship.
Research trends and future perspectives
So far, the review has observed some trends in the various
research efforts to improve on the adsorption of H & P from our
environment. A wide variety of carbonaceous adsorbents, agricul-
tural waste adsorbents, industrial waste adsorbents, inorganic
material adsorbents, polymeric adsorbents, bio-adsorbents, and
nano-adsorbents [141] has been studied for the adsorption of H & P
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 5
Reported and estimated adsorption attributes of the reviewed experiments.

S/ H&P Sorbent q Surface Effective surf. Moles of Volume of Solubility Moles in qp Ref.
N mass area area sorbent solution solution
(g) (mol/g) (m2/g) (mol/m2) (mol) L (mol/L) (mol) (Sorbent/
sol)
2,4-D
1 2,4-D 0.2 2.28E- 5.3 4.30E-05 4.56E-05 0.05 2.44E-03 1.22E-04 0.373 [27]
04
2 2,4-D 0.08 4.83E- 1.228 3.93E-03 3.86E-04 0.04 2.44E-03 9.77E-05 3.952 [39]
03
3 2,4-D 0.05 2.33E- 569 4.10E-06 1.17E-04 0.05 2.44E-03 1.22E-04 0.955 [41]
03
4 2,4-D 0.002 1.24E- 1288 9.59E-07 2.47E-06 0.02 2.44E-03 4.89E-05 0.051 [44]
03
5 2,4-D 0.002 1.66E- 1189 1.40E-06 3.32E-06 0.02 2.44E-03 4.89E-05 0.068 [44]
03
6 2,4-D 1 6.06E- 1.1 5.51E-04 6.06E-04 1 2.44E-03 2.44E-03 0.248 [28]
04
7 2,4-D 0.02 5.03E- 89.5 5.62E-06 1.01E-05 0.02 2.44E-03 4.89E-05 0.206 [33]
04
8 2,4-D 0.01 4.09E- 319 1.28E-06 4.09E-06 0.01 2.44E-03 2.44E-05 0.167 [38]
04
9 2,4-D 0.1 1.56E- 1225 1.27E-06 1.56E-04 0.1 2.44E-03 2.44E-04 0.639 [29]
03
10 2,4-D 0.1 1.49E- 1201 1.24E-06 1.49E-04 0.1 2.44E-03 2.44E-04 0.610 [29]
03
11 2,4-D 0.002 3.48E- 182 1.91E-06 6.97E-07 0.01 2.44E-03 2.44E-05 0.029 [36]
04
12 2,4-D 0.002 1.49E- 27.4 5.45E-06 2.99E-07 0.01 2.44E-03 2.44E-05 0.012 [36]
04
13 2,4-D 0.2 1.08E- 763 1.41E-06 2.15E-04 0.2 2.44E-03 4.89E-04 0.441 [31]
03
Others
14 2,4-DP 0.05 8.79E- 569 1.54E-06 4.40E-05 0.05 1.43E-03 7.14E-05 0.616 [41]
04
15 2,4,5-T 0.05 1.63E- 569 2.86E-06 8.15E-05 0.05 1.05E-03 5.24E-05 1.555 [41]
03
16 2-CPA 0.04 2.25E- 762 2.95E-06 9.00E-05 0.1 6.86E-03 6.86E-04 0.131 [92]
03
17 3-BrPP 0.04 2.44E- 762 3.20E-06 9.76E-05 0.1 – – – [92]
03
18 4-BrPP 0.04 2.10E- 762 2.76E-06 8.40E-05 0.1 – – – [92]
03
19 4-CPA 0.04 3.34E- 762 4.38E-06 1.34E-04 0.1 6.86E-03 6.86E-04 0.195 [92]
03
20 4-FPP 0.04 2.04E- 762 2.68E-06 8.16E-05 0.1 – – – [92]
03
21 8-Quinoline-carboxylic 0.5 3.78E- 32 1.18E-05 1.89E-04 0.05 2.00E-02 9.99E-04 0.189 [126]
acid 04
22 8-Quinoline-carboxylic 0.5 3.90E- 140 2.79E-06 1.95E-04 0.05 2.00E-02 9.99E-04 0.195 [126]
acid 04
23 8-Quinoline-carboxylic 0.5 4.38E- 161 2.72E-06 2.19E-04 0.05 2.00E-02 9.99E-04 0.219 [126]
acid 04
24 Acetamiprimid 0.2 8.67E- 673 1.29E-07 1.73E-05 0.05 1.91E-02 9.54E-04 0.018 [62]
05
25 Aldicarb 0.05 2.22E- 2500 8.86E-07 1.11E-04 1 2.59E-02 2.59E-02 0.004 [47]
03
26 Ametryn 0.05 1.56E- 2500 6.24E-07 7.80E-05 1 1.28E-03 1.28E-03 0.061 [47]
03
27 Ametryn 0.05 1.56E- 2500 6.24E-07 7.80E-05 1 1.28E-03 1.28E-03 0.061 [47]
03
28 Atrazine 0.1 3.46E- 70.54 4.91E-07 3.46E-06 0.025 3.25E-03 8.11E-05 0.043 [51]
05
29 Atrazine 0.04 4.78E- 5.77 8.29E-06 1.91E-06 0.025 3.25E-03 8.11E-05 0.024 [54]
05
30 Atrazine 0.3 4.34E- 1.59 2.73E-03 1.30E-03 0.01 3.25E-03 3.25E-05 40.119 [58]
03
31 Atrazine 0.2 6.72E- 673 9.99E-08 1.34E-05 0.05 3.25E-03 1.62E-04 0.083 [62]
05
32 Bentazon 0.5 2.08E- 27.28 7.63E-05 1.04E-03 0.02 2.37E-03 4.74E-05 21.930 [63]
03
33 Bromopropylate 0.2 4.41E- 630 7.01E-10 8.83E-08 0.05 2.34E-07 1.17E-08 7.560 [127]
07
34 Bromopropylate 0.2 2.87E- 600 4.79E-10 5.75E-08 0.05 2.34E-07 1.17E-08 4.920 [127]
07
35 Bromopropylate 0.2 2.71E- 570 4.75E-10 5.42E-08 0.05 2.34E-07 1.17E-08 4.640 [127]
07
36 Bromopropylate 0.2 490 3.77E-10 3.69E-08 0.05 2.34E-07 1.17E-08 3.160 [127]

132
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun Journal of Industrial and Engineering Chemistry 93 (2021) 117–137

Table 5 (Continued)
S/ H&P Sorbent q Surface Effective surf. Moles of Volume of Solubility Moles in qp Ref.
N mass area area sorbent solution solution
(g) (mol/g) (m2/g) (mol/m2) (mol) L (mol/L) (mol) (Sorbent/
sol)
1.85E-
07
37 Carbofuran 0.2 5.88E- 673 8.73E-08 1.18E-05 0.05 1.59E-03 7.93E-05 0.148 [62]
05
38 Diazinon 1 8.88E- 181.1 4.90E-07 8.88E-05 1 3.29E-03 3.29E-03 0.027 [115]
05
39 Dicamba 0.03 1.14E- 876 1.30E-06 3.42E-05 0.025 2.04E-02 5.09E-04 0.067 [103]
03
40 Dicamba 0.03 1.26E- 2345 5.38E-07 3.79E-05 0.025 2.04E-02 5.09E-04 0.074 [102]
03
41 Dimethoate 0.2 6.41E- 673 9.53E-08 1.28E-05 0.05 2.18E-02 1.09E-03 0.012 [62]
05
42 Dinoseb 0.05 1.26E- 2500 5.03E-07 6.28E-05 1 2.08E-04 2.08E-04 0.302 [47]
03
43 Diquat 0.01 1.38E- 142.2 9.73E-07 1.38E-06 0.025 3.84E+00 9.61E-02 0.00001 [65]
04
44 Diuron 0.5 6.32E- 5.771 1.10E-05 3.16E-05 0.025 1.80E-04 4.50E-06 7.019 [68]
05
45 Diuron 0.05 2.02E- 714 2.82E-09 1.01E-07 0.05 1.80E-04 9.01E-06 0.011 [67]
06
46 Diuron 0.05 9.14E- 2500 3.66E-07 4.57E-05 1 1.80E-04 1.80E-04 0.254 [47]
04
47 HCH 0.025 2.23E- 1840 1.21E-06 5.59E-05 0.1 2.51E-05 2.51E-06 22.260 [131]
03
48 Imazapic 10 7.14E- 1.46 4.89E-05 7.14E-04 0.02 7.99E-04 1.60E-05 44.659 [104]
05
49 Imazapic 10 6.36E- 1.99 3.20E-05 6.36E-04 0.02 7.99E-04 1.60E-05 39.818 [104]
05
50 Imazapyr 10 9.38E- 1.46 6.43E-05 9.38E-04 0.02 4.32E-02 8.65E-04 1.085 [104]
05
51 Imazapyr 10 8.00E- 1.99 4.02E-05 8.00E-04 0.02 4.32E-02 8.65E-04 0.924 [104]
05
52 Imidacloprid 0.3 1.51E- 1.59 9.53E-04 4.54E-04 0.01 2.00E-03 2.00E-05 22.771 [58]
03
53 MCPA 0.1 7.02E- 1225 5.73E-06 7.02E-04 0.1 4.11E-03 4.11E-04 1.707 [29]
03
54 MCPA 0.1 7.42E- 1201 6.18E-06 7.42E-04 0.1 4.11E-03 4.11E-04 1.804 [29]
03
55 MCPA 0.05 2.07E- 569.5 3.63E-06 1.03E-04 0.05 4.11E-03 2.06E-04 0.503 [41]
03
56 MCPA 0.002 1.99E- 1288 1.55E-06 3.99E-06 0.02 4.11E-03 8.22E-05 0.048 [44]
03
57 MCPP 0.05 2.68E- 569.5 4.70E-06 1.34E-04 0.05 4.10E-03 2.05E-04 0.653 [41]
03
58 Methyl parathion 0.1 2.40E- 23.4 1.03E-06 2.40E-06 0.1 1.43E-04 1.43E-05 0.168 [135]
05
59 Methyl parathion 0.5 2.77E- 0.91 3.04E-05 1.38E-05 0.025 1.43E-04 3.58E-06 3.862 [134]
05
60 Metribuzin 0.2 1.04E- 1.1 9.46E-04 2.08E-04 0.2 5.60E-03 1.12E-03 0.186 [81]
03
61 Metribuzin 0.2 9.57E- 4.2 2.28E-04 1.91E-04 0.2 5.60E-03 1.12E-03 0.171 [81]
04
62 Nicosulfuron 0.2 2.83E- 673 4.20E-08 5.65E-06 0.05 1.80E-02 9.02E-04 0.006 [62]
05
63 Oxamyl 0.6 5.70E- 1221 4.67E-07 3.42E-04 0.02 1.28E-03 2.55E-05 13.393 [121]
04
64 Oxamyl 1 2.85E- 75.22 3.79E-05 2.85E-03 0.1 1.28E-03 1.28E-04 22.321 [122]
03
65 Tebuthiuron 0.05 9.37E- 377.8 2.48E-06 4.68E-05 0.01 1.09E-02 1.09E-04 0.428 [108]
04
66 Tebuthiuron 0.05 8.18E- 245.7 3.33E-06 4.09E-05 0.01 1.09E-02 1.09E-04 0.374 [108]
04

in recent times. The use of carbonized biomass (biochar or
activated carbon) and non-carbonized biomass (biosorbent) has
had a long history but is still being used until now (to positive
effect) [142,143]. Much of the biomass used is agricultural wastes
and residues from cultivation and processing activities. Natural
materials with adsorption potentials include peels, husks, shav-
ings, starch, fibers, leaves, corks, and shells. Nowadays, studies are
driven toward finding ways to modify these biomasses for more
improved performance chemically. The major advantage of using
biomass, in this case, is ready-availability and low-cost [144–146].
Another area of interest in recent times is the use of modified and
unmodified clays as adsorbents. Clays such as montmorillonite
[39,50,94,126], sepiolite, illite, palygorskite, muscovite [61],
kaolinite [100], and bentonite [27,95,113] have been investigated.

133
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
Fig. 4. Trend relationships among adsorption capacity, specific surface area, effective surface area, and preferential adsorption of (a) the various adsorbents (of different
RMM.) toward 2,4-D, and (b) activated carbon towards various P & H, based on the S/N 1–13, and 1–66 in Table 5, respectively. Note that S/N is used instead of Ref. to distinguish
between different experiments reported in the same reference paper.
These clays are also ameliorable to chemical modification toward
achieving better adsorption capacity and selectivity.
Also, synthetic and organic-based polymers for the sorption of
H & P are gaining research popularity in recent times. Synthetic
polymers so far investigated include molecularly imprinted
polystyrene [60], polyurethane [66,85], poly(methacrylic acid–
trimethylolpropane trimethacrylate) [108], and organic-based
polymers like cyclodextrin [119]. In the future, we expect that
other kinds of polymers with more novel modification techniques
to be investigated for herbicide and pesticide removal potentials.
Nanotechnology is the other area that is also gaining interest in
pesticide and herbicide sorption. Nanoparticles (particles with
sizes between 1 and 100 nm) possess a large surface area that can
be modified for improved selectivity [147]. Carbon-based nano-
particles (such as carbon nanotubes [65,71], MWCNTs [65,97],
graphene [32,36,121], and graphene oxide [69,72,119]), metals
[46,52,107,137] and clays [63] have high potentials for the
removing H & P from water.
Regarding the methodology, several approaches have been
documented already. However, the use of spent adsorbent from
metal sorption to remove H & P is an interesting approach recently
evaluated by Ramrakhiani et al. [74]. The biosorbent was stable as
the metal desorption during the adsorption experiments were
below regulatory limits. Such a study provides a platform for more
investigations in this direction. Another study was able to prove
that the chemical impregnation of adsorbents with heavy metals
(Cu(II) in this case) would increase the selective adsorption toward
the H & P, albeit linuron in this case [79].
The competitive adsorption of several H & P in aqueous media
was investigated recently [37]. Studies such as this determine the
134
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
adsorbent performance of real wastewater scenarios and industrial
applications [148,149]. It is suggested that more competitive
adsorption studies be conducted for H &P, especially with popular
competitive species in the soil, such as humic acid [38,150]. This
form of investigation is imperative in contaminant hydrology.
Other studies have used a combination of photo-degradation
and adsorption [69,76,87] in H & P removal from solution. In such
cases, the photo-catalyst TiO2 was impregnated or precipitated
onto the matrix of the adsorbent. These are hybrid processes that
combine several techniques to achieve optimum performance.
Finally, temperature swing adsorption (TSA) is a popular gas-phase
technique. However, a recent study has successfully adapted the
methodology for herbicides adsorption in aqueous phase [49]. The
process also involves in situ adsorbent regeneration, making it
more amenable to industrial applications.
The adsorption mechanism can also be investigated using
computational studies [151]. Molecular interactions are difficult to
elucidate with experimental results [152]. Hence computational
studies are used for molecular simulation and modeling [153].
Density functional theory (DFT) is used to elucidate the adsorption
mechanism and chemical interactions between adsorbate and
adsorbent species [154,155]. Computational chemistry is an
interesting area for future H & P adsorption studies.
The safe disposal of used adsorbent is another interesting area
that could be investigated. Ramrakhiani et al. [74] investigated the
safe disposal of biosorbent from waste activated sludge used for
glyphosate adsorption. Positive results were achieved using the
technique of inertization in a glass matrix. Other reported
techniques involve stabilization in a polymeric resin [144] or a
cementitious binder [156].
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
Table 6
Correlation data among reported and derived adsorption properties of prominent adsorbate and adsorbents.
Adsorption properties Sorbent mass vs moles in solution q vs SBET
Sorbate/sorbent
All
0.0486 0.2624
2,4-D 0.9865 0.1231
Clay 0.8389
0.1493
Biochar
0.7008 0.2819
AC
0.0780 0.1563
Conclusion
We have discussed recent research advances in the mitigation
of herbicide and pesticide (H & P) pollution via adsorption. This
paper focused majorly on contemporary literature and discussed
the research findings based on each chemical species. Numerous
carbonaceous adsorbents, agricultural waste adsorbents, industri-
al waste adsorbents, inorganic material adsorbents, polymeric
adsorbents, bio-adsorbents, and nano-adsorbents have been
studied for H & P pollution remediation in recent times. Although
a wide variety of pollutants have been studied, 2.4-D and atrazine
evinced a significantly larger research interest than other
herbicides and pesticides, respectively. Their popularity is
attributed to their wider applications and efficiency in farming.
Further, we identified the newly derived adsorption attributes (the
effective surface area (eSBET) and the dimensionless preferential
adsorption (qp)) as more accurate in informing on the sorbate-
sorbent interface than the conventional specific surface area (SBET)
and adsorption capacity (q). And, via correlation analysis, we
confirmed the accuracy and significance of the new attributes
toward designing future adsorption systems. Thence, adsorption is
undoubted as an excellent technique for mitigating H & P pollution
in aqueous environments. Future research could use spent, heavy
metal-laden adsorbents, photo-assisted adsorption to improve
competitive adsorption of H & P. Conclusively, adsorption is
available for performance optimization based on the novel
adsorption attributes provided in this review.
Author contribution statement
JOI initiated and wrote the literature review and carried out
data extraction; AGA conceptualized, moderated, and provided
resource materials for the review; AAA coordinated, organized,
structured, and conceived the adsorption attributes section. AAA
and JOI did the statistical analysis. AAA handled the editorial work
and the graphical abstract. JOI and AAA constructed the Tables.
Compliance with ethical standards
This article does not contain any studies involving humans or
animals performed by any authors.
Funding
This work was self-funded by the authors; no external funding
was sourced nor received.
Conflict of interest
The authors declare that there are no conflicts of interest.
Acknowledgments
We are grateful to our families and colleagues at the depart-
ments for their moral support throughout the research period.
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
eSBET vs qp Moles of sorbent vs qp SBET vs eSBET Sorbent mass v eSBET q vs eSBET
0.2848 0.5553
0.2240
0.0376 0.3844
0.9508 0.4693
0.3414 0.0731 0.8271
0.0477 0.9720
0.2534
0.4359 0.9039

0.4622 0.2367
0.3160
0.8061 0.8135
0.6225 0.6147
0.2733 0.8169 0.3619
Appendix A. Supplementary data
Supplementary material related to this article can be found, in
the online version, at doi:https://doi.org/10.1016/j.jiec.2020.10.011.
References
[1] S. Cosgrove, B. Jefferson, P. Jarvis, Environ. Technol. Rev. 8 (2019) 1.
[2] M. Roser, Pesticides Our World in Data, (2019) . https://ourworldindata.org/
pesticides.
[3] A. Khan, J. Wang, J. Li, X. Wang, Z. Chen, A. Alsaedi, T. Hayat, Y. Chen, X. Wang,
Environ. Sci. Pollut. Res. 24 (2017) 7938.
[4] H. Pang, Y. Wu, X. Wang, B. Hu, X. Wang, Chem. Asian J. 14 (15) (2019) 2542.
[5] K. Foo, B. Hameed, J. Hazard. Mater. 175 (2010) 1.
[6] J.O. Ighalo, A.G. Adeniyi, Chemosphere 260 (2020) 127569, doi:http://dx.doi.
org/10.1016/j.chemosphere.2020.127569.
[7] J.O. Ighalo, A.G. Adeniyi, E.O. Oke, L.T. Adewiye, F.O. Motolani, Eur. J. Sustain.
Dev. Res. 4 (2020), doi:http://dx.doi.org/10.29333/ejosdr/8302.
[8] J.O. Ighalo, A.G. Adeniyi, J. Water Process Eng. 35 (2020) 101228, doi:http://
dx.doi.org/10.1016/j.jwpe.2020.101228.
[9] L. Hevira, R. Zilfa, J.O. Ighalo, R. Zein, J. Environ. Chem. Eng. 8 (2020) 104290,
doi:http://dx.doi.org/10.1016/j.jece.2020.104290.
[10] S. Ahmadi, C.A. Igwegbe, Appl. Water Sci. 8 (2018) 170.
[11] S. Ahmadi, L. Mohammadi, C.A. Igwegbe, S. Rahdar, A.M. Banach, Int. J. Ind.
Chem. 9 (2018) 241.
[12] S. Liu, C. Lai, B. Li, C. Zhang, M. Zhang, D. Huang, L. Qin, H. Yi, X. Liu, F. Huang,
Chem. Eng. J. 384 (2020) 123304.
[13] X. Zhou, Z. Zeng, G. Zeng, C. Lai, R. Xiao, S. Liu, D. Huang, L. Qin, X. Liu, B. Li,
Chem. Eng. J. 383 (2020) 123091.
[14] L. Li, C. Lai, F. Huang, M. Cheng, G. Zeng, D. Huang, B. Li, S. Liu, M. Zhang, L. Qin,
Water Res. 160 (2019) 238.
[15] J. Derco, B. Vrana, Biosorption, Biosorption, Intech Open, London, UK, 2018,
doi:http://dx.doi.org/10.5772/intechopen.78961 1.
[16] A.G. Adeniyi, J.O. Ighalo, J. Environ, Chem. Eng. 7 (2019) 103100, doi:http://dx.
doi.org/10.1016/j.jece.2019.103100.
[17] I. Anastopoulos, A. Robalds, H.N. Tran, D. Mitrogiannis, D.A. Giannakoudakis,
A. HosseiniBandegharaei, G.L. Dotto, Environ. Chem. Lett. 17 (2018) 755, doi:
http://dx.doi.org/10.1007/s10311-018-00829-x.
[18] I. Anastopoulos, A. Bhatnagar, D.N. Bikiaris, G.Z. Kyzas, Int. J. Mol. Sci. 18
(2017) 114, doi:http://dx.doi.org/10.3390/ijms18010114.
[19] O.A.A. Eletta, J.O. Ighalo, J. Res, Inf. Civil Eng. 16 (2019) 2479, doi:http://dx.doi.
org/10.13140/RG.2.2.20511.61604.
[20] S. Ahmed, M. Ahmad, B.L. Swami, S. Ikram, J. Adv. Res. 7 (2016) 17.
[21] D. Sushman, S. Richa, Int. Res. J. Environ. Sci. 4 (2015) 103.
[22] A. Mojiri, J.L. Zhou, B. Robinson, A. Ohashi, N. Ozaki, T. Kindaichi, H. Farraji, M.
Vakili, Chemosphere 253 (2020) 126646.
[23] J.O. Ighalo, A.G. Adeniyi, Waste Dispos. Sustain. Energy 2 (2020) 161, doi:
http://dx.doi.org/10.1007/s42768-020-00043-y.
[24] C. Verma, E.E. Ebenso, I. Bahadur, M. Quraishi, J. Mol. Liq. 266 (2018) 577.
[25] O. Onafeso, A. Olusola, Urban stone decay and sustainable built environment
in the Niger River Basin, Urban Geomorphology, Elsevier, Amsterdam,
Netherlands, 2018 p. 261.
[26] M. Blachnio, A. Derylo-Marczewska, M. Seczkowska, Influence of pesticide
properties on adsorption capacity and rate on activated carbon from aqueous
solution, Sorption in 2020s, IntechOpen, London, UK, 2019.
[27] F.M. De Souza, O.A.A. dos Santos, M.G.A. Vieira, Environ. Sci. Pollut. Res. Int. 26
(2019) 18329, doi:http://dx.doi.org/10.1007/s11356-019-05196-w.
[28] M. Essandoh, D. Wolgemuth, C.U. Pittman Jr, D. Mohan, T. Mlsna, Chemo-
sphere 174 (2017) 49.
[29] M.M. Abdeldaiem, J. Rivera-Utrilla, M. Sánchez-Polo, R. Ocampo-Pérez, Sci.
Total Environ. 537 (2015) 335.
[30] K. Chair, A. Bedoui, N. Bensalah, F.J. Fernández-Morales, C. Sáez, P. Cañizares,
M.A. Rodrigo, J. Chem. Technol. Biotechnol. 92 (2017) 83.
[31] B. Hameed, J. Salman, A. Ahmad, J. Hazard. Mater. 163 (2009) 121.
[32] R. Kamaraj, A. Pandiarajan, M.R. Gandhi, A. Shibayama, S. Vasudevan,
ChemistrySelect 2 (2017) 342.
[33] O. Kazak, Y.R. Eker, I. Akin, H. Bingol, A. Tor, Environ. Sci. Pollut. Res. 24 (2017)
23057.
[34] J.P. Kearns, D.R. Knappe, R.S. Summers, Environ. Eng. Sci. 32 (2015) 912.
135
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
[35] J.P. Kearns, K.K. Shimabuku, D.R. Knappe, R.S. Summers, Environ. Eng. Sci. 36
(2019) 710.
[36] M. Khoshnood, S. Azizian, J. Ind. Eng. Chem. 18 (2012) 1796.
[37] B.Y. Kumar, N. Singh, S.B. Singh, Indian J. Chem. Technol. 24 (2017) 400.
[38] A. Kurtog lu, G. Atun, Desalin. Water Treat. 57 (2016) 25653.
[39] C.V.L. Natarelli, P.I.C. Claro, K.W.E. Miranda, G.M.D. Ferreira, J.E. de Oliveira, J.
M. Marconcini, SN Appl. Sci. 1 (2019) 1212.
[40] V. Okumuş, K.S. Çelik, S. Özdemir, A. Dündar, E. Kılınç, Desalin. Water Treat.
56 (2015) 1898.
[41] A. Pandiarajan, R. Kamaraj, S. Vasudevan, S. Vasudevan, Bioresour. Technol.
261 (2018) 329.
[42] Y. Qui, X. Yuxiao, H. Cheng, Z. Zhou, G.D. Sheng, Environ. Sci. Technol. 43
(2009) 4973.
[43] J.M. Salman, A.J. Khadim, J. Al-Nisour Univ. Coll. 1 (2017) 1.
[44] A. Spaltro, M. Pila, S. Simonetti, S. Álvarez-Torrellas, J.G. Rodríguez, D. Ruiz, A.
D. Compañy, A. Juan, P. Allegretti, J. Contam. Hydrol. 218 (2018) 84.
[45] T. Zhou, L. Fang, X. Wang, M. Han, S. Zhang, R. Han, Desalin. Water Treat. 70
(2017) 294.
[46] I. Ali, Z.A. AL-Othman, A. Alwarthan, J. Mol. Liq. 221 (2016) 1168.
[47] E. Ayranci, N. Hoda, Chemosphere 60 (2005) 1600.
[48] F. Suo, X. You, Y. Ma, Y. Li, Chemosphere 235 (2019) 918.
[49] B. Aumeier, H. Dang, M. Wessling, Preliminary study on the application of
temperature swing adsorption in aqueous phase for pesticide removal,
International Conference on Environment and Renewable Energy, IOP
Publishing, Da Nang, Vietnam, 2018 1.
[50] Z. Gu, M. Gao, L. Lu, Y. Liu, S. Yang, Ind. Eng. Chem. Res. 54 (2015) 4947.
[51] P.F. Coldebella, M.R. Fagundes-Klen, L. Nishi, K.C. Valverde, E.B. Cavalcanti, O.
A. Andreo dos Santos, R. Bergamasco, Can. J. Chem. Eng. 95 (2017) 961.
[52] I. Ali, Z. Alothman, A. Al-Warthan, Int. J. Environ. Sci. Technol. 13 (2016) 733.
[53] X. Chen, Q. Zhou, F. Liu, Q. Peng, P. Teng, Chemosphere 233 (2019) 49.
[54] L.F. Cusioli, C.D.O. Bezerra, H.B. Quesada, A.T. Alves Baptista, L. Nishi, M.F.
Vieira, R. Bergamasco, Environ. Technol. (August) (2019) 1, doi:http://dx.doi.
org/10.1080/09593330.2019.1653381.
[55] N.C. Homem, A.M.S. Vieira, R. Bergamasco, M.F. Vieira, Can. J. Chem. Eng. 96
(2018) 1468.
[56] M. Hussein, A. Abdullah, N. Badr El-Din, E. Mishaqa, J. Fertil. Pestic. 8 (2017)
177.
[57] S. Li, J. Lü, T. Zhang, Y. Cao, J. Li, Water Sci. Technol. 75 (2016) 482.
[58] A. Mandal, N. Singh, J. Environ. Sci. Health B 51 (2016) 192, doi:http://dx.doi.
org/10.1080/03601234.2015.1108817.
[59] F. Okeola, F. Nwosu, O. Ameen, T. Abu, A. Mohammed, A. Ibrahim, O. Amusa, J.
Org. Chem. 12 (2017) 219.
[60] F. Ruggieri, A.A. D’Archivio, D. Di Camillo, L. Lozzi, M. Maggi, R. Mercorio, S.
Santucci, J. Sep. Sci. 38 (2015) 1402.
[61] M. Sanchez-Martin, M. Rodriguez-Cruz, M. Andrades, M. Sanchez-Camazano,
Appl. Clay Sci. 31 (2006) 216.
[62] M.M. Vuk9 cevic, A.M. Kalijadis, T.M. Vasiljevi
c, B.M. Babi
c, Z.V. Lauševi
c, M.D,
Microporous Mesoporous Mater. 214 (2015) 156.
[63] M. Shirzad-Siboni, A. Khataee, A. Hassani, S. Karaca, Comptes Rendus Chim.
18 (2015) 204.
[64] M.C. Bruzzoniti, R.M. De Carlo, L. Rivoira, M. Del Bubba, M. Pavani, M. Riatti, B.
Onida, Environ. Sci. Pollut. Res. 23 (2016) 5399.
[65] O. Duman, C. Özcan, T.G. Polat, S. Tunç, Environ. Pollut. 244 (2019) 723.
[66] J.O. Vinhal, K.K. Nege, M.R. Lage, J.W.d.M. Carneiro, C.F. Lima, R.J. Cassella,
Ecotoxicol. Environ. Saf. 145 (2017) 597.
[67] M. Al Bahri, L. Calvo, M. Gilarranz, J. Rodriguez, Chem. Eng. Commun. 203
(2016) 103.
[68] C.d.O. Bezerra, L.F. Cusioli, H.B. Quesada, L. Nishi, D. Mantovani, M.F. Vieira, R.
Bergamasco, Environ. Technol. 4 (2018) 191, doi:http://dx.doi.org/10.1080/
09593330.2018.1493148.
[69] X. Liu, H. Hong, X. Wu, Y. Wu, Y. Ma, W. Guan, Y. Ye, Water Air Soil Pollut. 227
(2016) 21.
[70] S. Salvestrini, J. Jovanovi c, B. Adnadjevi c, Desalin. Water Treat. 57 (2016)
22868.
[71] I. Ali, O.M. Alharbi, Z.A. ALOthman, A.M. Al-Mohaimeed, A. Alwarthan,
Environ. Res. 170 (2019) 389.
[72] Q. Yang, J. Wang, W. Zhang, F. Liu, X. Yue, Y. Liu, M. Yang, Z. Li, J. Wang, Chem.
Eng. J. 313 (2017) 19.
[73] R.T. Carneiro, T.B. Taketa, R.J.G. Neto, J.L. Oliveira, E.V. Campos, M.A. de
Moraes, C.M. da Silva, M.M. Beppu, L.F. Fraceto, J. Environ. Manage. 151 (2015)
353.
[74] L. Ramrakhiani, S. Ghosh, A.K. Mandal, S. Majumdar, Chem. Eng. J. 361 (2019)
1063.
[75] L. Rivoira, M. Appendini, S. Fiorilli, B. Onida, M. Del Bubba, M.C. Bruzzoniti,
Environ. Sci. Pollut. Res. 23 (2016) 21682.
[76] M.M. Dávila-Jiménez, M.P. Elizalde-González, E. García-Díaz, A.M. Santes-
Aquino, Phys. Chem. Earth 91 (2016) 77.
[77] L. Rissouli, M. Benicha, M. Chabbi, J. Mater. Environ. Sci. 7 (2016) 531.
[78] L.S. Belaroui, A. Ouali, A. Bengueddach, A.L. Galindo, A. Peña, Appl. Clay Sci.
164 (2018) 26.
[79] M. Khalfaoui, A. El Ghali, C. Aguir, Z. Mohamed, M.H.V. Baouab, A.B. Lamine,
Ind. Crop Prod. 67 (2015) 169.
[80] R. Kamaraj, A. Pandiarajan, S. Vasudevan, S. Vasudevan, J. Environ. Chem. Eng.
6 (2018) 2017.
[81] M. Essandoh, D. Wolgemuth, C.U. Pittman, D. Mohan, T. Mlsna, Environ. Sci.
Pollut. Res. 24 (2017) 4577.
136
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
[82] M. Behloul, H. Lounici, N. Abdi, N. Drouiche, N. Mameri, Int. Biodeterior.
Biodegrad. 119 (2017) 687.
[83] O. Kitous, N. Abdi, H. Lounici, H. Grib, N. Drouiche, E. Benyoussef, N. Mameri,
Desalin. Water Treat. 57 (2016) 1865.
[84] S. Jodeh, G. Hanbali, S. Tighadouini, S. Radi, O. Hamed, D. Jodeh, BMC Chem. 13
(2019) 86.
[85] J.O. Vinhal, M.R. Lage, J.W.M. Carneiro, C.F. Lima, R.J. Cassella, J. Environ.
Manage. 156 (2015) 200.
[86] T. Zhou, N. Song, H. Yu, Y.-W. Yang, Langmuir 31 (2015) 1454.
[87] N.T.K. Phuong, M.-W. Beak, B.T. Huy, Y.-I. Lee, Chemosphere 146 (2016) 51.
[88] I.-G. Cara, B.-G. Rusu, L. Raus, G. Jitareanu, Chemosphere 186 (2017) 360.
[89] J. Casarin, A.C. Gonçalves Jr, M.G. Segatelli, C.R.T. Tarley, React. Funct. Polym.
121 (2017) 101.
[90] J.O. Ighalo, J.O. Ajala, G. Umunweke, S. Ogunniyi, C.A. Adeyanju, C.A. Igwegbe,
A.G. Adeniyi, J. Environ. Chem. Eng. 8 (2020) 104264, doi:http://dx.doi.org/
10.1016/j.jece.2020.104264.
[91] J.O. Ighalo, A.G. Adeniyi, ChemBioEng Rev. 7 (2020) 50, doi:http://dx.doi.org/
10.1002/cben.201900020.
[92] A. Derylo-Marczewska, M. Blachnio, A.W. Marczewski, M. Seczkowska, B.
Tarasiuk, Chemosphere 214 (2019) 349.
[93] X. Huang, S. Feng, G. Zhu, W. Zheng, C. Shao, N. Zhou, Q. Meng, Int. J. Biol.
Macromol. 149 (2020) 882.
[94] L.M. Kaluperovi c, Z.P. Tomi
c, R.D. Ðurovi c-Pej9cev, P.J. Vuli
c, D.P. Ašanin, J.
Environ. Sci. Health B 52 (2017) 291.
[95] Z.P. Tomi c, D.P. AŠanin, R. Ðurovi cev, A. ÐorÐevi
c-Pej9 c, P. Makreski, Spectrosc.
Lett. 48 (2015) 685.
[96] T.R. De Aguiar Jr, J.O.A.G. Neto, U. Şen, H. Pereira, Heliyon 5 (2019)e01189.
[97] A.A. D’Archivio, M.A. Maggi, A. Odoardi, S. Santucci, M. Passacantando,
Nanotechnology 29 (2018)065701.
[98] J.M. Park, S.H. Jhung, J. Hazard. Mater. 396 (2020) 122624.
[99] F. Bruna, I. Pavlovic, C. Barriga, J. Cornejo, M. Ulibarri, Appl. Clay Sci. 33 (2006)
116.
[100] F.O. Nwosu, O.J. Ajala, F.O. Okeola, S.A. Adebayo, O.K. Olanlokun, O.A.A. Eletta,
Egypt. J. Aquat. Res. 45 (2019) 99, doi:http://dx.doi.org/10.1016/j.
ejar.2019.05.005.
[101] H. Nefzi, L.L. El Atrache, J. Mater. Environ. Sci. 9 (2018) 1614.
[102] M. Pinto, R. Santos, R. Gonçalves, V. Duarte, P. Borges, F. Leroux, V.
Constantino, C. Izumi, F. Pinto, J. Tronto, Dalton Trans. 47 (2018) 3119.
[103] M.d.C.E. Pinto, R.G.L. Gonçalves, R.M.M. dos Santos, E.A. Araújo, G.F. Perotti, R.
dos Santos Macedo, M.A. Bizeto, V.R.L. Constantino, F.G. Pinto, J. Tronto,
Microporous Mesoporous Mater. 225 (2016) 342.
[104] S. Yavari, A. Malakahmad, N.B. Sapari, S. Yavari, J. Environ, Chem. Eng. 4 (2016)
3981.
[105] S. Yavari, M. Abualqumboz, N. Sapari, H.-A. Hata-Suhaimi, N.-Z. Nik-Fuaad,
Int. J. Environ. Sci. Technol. 17 (2020) 3341.
[106] A. Jevremovi c, P. Bober, M. Mi9 cušík, J. Kuli9cek, U. Acharya, J. Pfleger, M.
Milojevi c-Raki c, D. Krajišnik, M. Trchová, J. Stejskal, Microporous Meso-
porous Mater. 287 (2019) 234.
[107] I. Ali, Z.A. Al-Othman, A. Al-Warthan, Desalin. Water Treat. 57 (2016) 10409.
[108] R.J. Da Fonseca, M.G. Segatelli, K.B. Borges, C.R.T. Tarley, React. Funct. Polym.
93 (2015) 1.
[109] A. Bakka, M. Ait Taleb, N. Saffaj, A. Laknifli, R. Mamouni, A. Benlhachemi, B.
Bakiz, Y. Diane, J. Eng. Sci. Technol. 13 (2018) 925.
[110] A. Bakka, R. Mamouni, N. Saffaj, A. Laknifli, A. Benlhachemi, B. Bakiz, M. El
Haddad, M.A. Taleb, A. Roudani, A. Faouzi, Sci. Study Res. Chem. Chem. Eng.
Biotechnol. Food Ind. 17 (2016) 271.
[111] Z. Al-Qodah, A. Shawaqfeh, W. Lafi, Adsorption 13 (2007) 73.
[112] M.H. Dehghani, S. Kamalian, M. Shayeghi, M. Yousefi, Z. Heidarinejad, S.
Agarwal, V.K. Gupta, Microchem. J. 145 (2019) 486.
[113] S. Heydari, L. Zare, H. Ghiassi, J. Appl, Res. Water Wastewater 6 (2019) 45.
[114] G. Moussavi, H. Hosseini, A. Alahabadi, Chem. Eng. J. 214 (2013) 172.
[115] N.M. Phuong, N.C. Chu, D. Van Thuan, M.N. Ha, N.T. Hanh, H.D.T. Viet, M. Thu,
N. Thi, P. Van Quan, T. Truc, J. Chem. 2019 (2019) 1.
[116] N.Y. Mezenner, H. Lagha, H. Kais, M. Trari, Appl. Water Sci. 7 (2017) 4067.
[117] M. Cobas, J. Meijide, M. Sanromán, M. Pazos, J. Taiwan Inst, Chem. E 61 (2016)
166.
[118] M.M. Kalhor, A.A. Rafati, L. Rafati, A.A. Rafati, J. Mol. Liq. 266 (2018) 453.
[119] G. Liu, L. Li, D. Xu, X. Huang, X. Xu, S. Zheng, Y. Zhang, H. Lin, Carbohydr. Polym.
175 (2017) 584.
[120] S.G. Mohammad, S.M. Ahmed, A.F.M. Badawi, Desalin. Water Treat. 55 (2015)
2109.
[121] S. Agarwal, N. Sadeghi, I. Tyagi, V.K. Gupta, A. Fakhri, J. Colloid Interface Sci.
478 (2016) 430.
[122] S.G. Mohammad, S.M. Ahmed, Int. J. Ind. Chem. 8 (2017) 121.
[123] R. Al-Shawabkah, Z. Al-Qodah, A. Al-Bsoul, Desalin. Water Treat. 53 (2015)
2555.
[124] A. Derylo-Marczewska, M. Blachnio, A.W. Marczewski, A. Swiatkowski, B.
Buczek, Chem. Eng. J. 308 (2017) 408.
[125] A.W. Marczewski, M. Seczkowska, A. Deryło-Marczewska, M. Blachnio,
Adsorption 22 (2016) 777.
[126] M. Mekhloufi, A. Zehhaf, A. Benyoucef, C. Quijada, E. Morallon, Environ.
Monit. Assess. 185 (2013) 10365.
[127] O.A. Ioannidou, A.A. Zabaniotou, G.G. Stavropoulos, M.A. Islam, T.A. Albanis,
Chemosphere 80 (2010) 1328.
[128] P.G. Moradeeya, M.A. Kumar, R.B. Thorat, M. Rathod, Y. Khambhaty, S. Basha,
Cellulose 24 (2017) 1319.
J.O. Ighalo, A.G. Adeniyi and A.A. Adelodun
[129] S. Sousa, P. Jiménez-Guerrero, A. Ruiz, N. Ratola, A. Alves, Environ. Technol. 32
(2011) 673.
[130] R. Farghali, M. Basiony, S. Gaber, H. Ibrahim, E. Elshehy, Arab. J. Chem. 13
(2020) 6730.
[131] K. Ignatowicz, Int. J. Heat Mass Transf. 54 (2011) 4931.
[132] S. Senthilkumaar, S. Krishna, P. Kalaamani, C. Subburamaan, N.G. Sub-
ramaniam, Mod. Appl. Sci. 4 (2010) 67.
[133] S. Singh, A. Jain, K.R. Tiwari, N. Kumar, R. Tomar, Int. J. Mater. Sci. 14 (2019) 17.
[134] A. N’diaye, C. Boudokhane, M. Elkory, M. Kankou, H. Dhaouadi, Water Sci.
Technol. Water Supply 18 (2017) 1545.
[135] G.Z. Memon, M. Bhanger, M. Akhtar, F.N. Talpur, J.R. Memon, Chem. Eng. J. 138
(2008) 616.
[136] P. Peng, Y.-H. Lang, X.-M. Wang, Ecol. Eng. 90 (2016) 225.
[137] N. Mansouriieh, M. Sohrabi, M. Khosravi, Int. J. Environ. Sci. Technol. 13 (2016)
1393.
[138] H.N. Tran, S.-J. You, A. Hosseini-Bandegharaei, H.-P. Chao, Water Res. 120
(2017) 88, doi:http://dx.doi.org/10.1016/j.watres.2017.04.014.
[139] M.S. Shafeeyan, M.S, W.M.A. Wan Daud, A. Houshmand, A. Shamiri, J. Anal.
Appl. Pyrolysis 89 (2010) 143.
[140] A.A. Adelodun, K.H. Kim, J.C. Ngila, J.E. Szulejko, Appl. Energy 158 (2015) 631.
[141] N. Tarannum, R. Khan, Cost-effective green materials for the removal of
pesticides from aqueous medium, Green Materials for Wastewater Treat-
ment, Springer, 2020, pp. 99.
[142] J.O. Ighalo, A.A.O. Eletta, Chem. Eng. Commun. (2020) 1, doi:http://dx.doi.org/
10.1080/00986445.2020.1771322.
[143] C.A. Igwegbe, O.D. Onukwuli, J.O. Ighalo, P.U. Okoye, Environ. Process. (2020)
1, doi:http://dx.doi.org/10.1007/s40710-020-00467-y.
137
Journal of Industrial and Engineering Chemistry 93 (2021) 117–137
[144] O.A.A. Eletta, A.G. Adeniyi, J.O. Ighalo, D.V. Onifade, F.O. Ayandele, Environ.
Technol. Rev. 9 (2020) 20, doi:http://dx.doi.org/10.1080/
21622515.2020.1730983.
[145] J.O. Ighalo, A.G. Adeniyi, SN Appl. Sci. 2 (2020) 509, doi:http://dx.doi.org/
10.1007/s42452-020-2335-x.
[146] J.O. Ighalo, A.A.O. Eletta, Appl. Water Sci. 10 (2020) 197, doi:http://dx.doi.org/
10.1007/s13201-020-01283-3.
[147] A.A.O. Eletta, A.G. Adeniyi, M.M. Magaji, J.O. Ighalo, FUOYE Science
Conference, Oye-Ekiti, Nigeria, 2019.
[148] J.O. Ighalo, I.O. Tijani, J.O. Ajala, F.O. Ayandele, O.A.A. Eletta, A.G. Adeniyi,
Recent Innov. Chem. Eng. 13 (2020), doi:http://dx.doi.org/10.2174/
2405520413999200623174612.
[149] J.O. Ighalo, A.G. Adeniyi, O.A.A. Eletta, L.T. Arowoyele, Indian Chem. E (2020),
doi:http://dx.doi.org/10.1080/00194506.2020.1787870.
[150] J.M. Arroyave, C.C. Waiman, G.P. Zanini, M.J. Avena, Chemosphere 145 (2016) 34.
[151] D. Wei, C. Zhao, A. Khan, L. Sun, Y. Ji, Y. Ai, X. Wang, Chem. Eng. J. 375 (2019)
121964.
[152] Y. Ai, Y. Liu, Y. Huo, C. Zhao, L. Sun, B. Han, X. Cao, X. Wang, Environ. Sci. Nano 6
(2019) 3336.
[153] K. Talha, B. Wang, J.-H. Liu, R. Ullah, F. Feng, J. Yu, S. Chen, J.-R. Li, J. Environ.
Chem. Eng. 8 (2020) 103642.
[154] N. Aarab, A. Hsini, A. Essekri, M. Laabd, R. Lakhmiri, A. Albourine, Groundw.
Sustain. Dev. 11 (2020) 100416.
[155] N. Aarab, M. Laabd, H. Eljazouli, R. Lakhmiri, H. Kabli, A. Albourine, Int. J. Ind.
Chem. 10 (2019) 269.
[156] C. Sullivan, M. Tyrer, C.R. Cheeseman, N.J. Graham, Sci. Total Environ. 408
(2010) 1770, doi:http://dx.doi.org/10.1016/j.scitotenv.2010.01.010.