Current Research in Green and Sustainable Chemistry 4 (2021) 100188

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Current Research in Green and Sustainable Chemistry

journal homepage: www.elsevier.com/journals/
current-research-in-green-and-sustainable-chemistry/2666-0865

Trends in the mitigation of heavy metal ions from aqueous solutions using
unmodified and chemically-modified agricultural waste adsorbents
Oluwafemi Ogunlalu a, Ifeoluwa Peter Oyekunle a, *, Kingsley O. Iwuozor b, c,
Abiodun Daniel Aderibigbe a, Ebuka Chizitere Emenike c
a
Department of Chemistry, Federal University of Technology, Akure, Ondo State, Nigeria
b
Department of Chemistry, University of Lagos, Lagos, Nigeria
c
Department of Pure and Industrial Chemistry, Nnamdi Azikiwe University, Awka, Nigeria

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

Keywords: One of the many methods that have been utilized in the remediation of heavy metals is adsorption. This paper
Chemical modification focuses specifically on the chemically-modified means of adsorption using several agricultural wastes as the
Isotherm adsorbents for the uptake of various heavy metal ions. This review focuses on the effect of chemical modification
Kinetic
on several agricultural wastes adsorbents for the uptake of various heavy metal ions, it examines the progress
Remediation
made over the years in the adsorption of heavy metal ions using unmodified and chemically-modified agricultural
Agricultural waste
Environmental issues wastes. Herein, we described the range of technologies for heavy metal remediation, the effect of chemical
modification of agricultural wastes, kinetic and isotherm studies, and the associated environmental issues. Our
findings revealed that the isotherm that best describes the adsorption process is the Langmuir isotherm followed
by the Freundlich isotherm and the kinetics was better described by the pseudo-second order model. Also, with
respect to the adsorption energy requirement, agricultural wastes such as eucalyptus wood/H2O2, Lansium
domesticum peel, and sugarcane bagasse showed some remarkable promises especially for industrial scale-up. As
regards the toxicity of the modifying agent, this review suggests that potassium carbonate should be assisted with
surface-improving additives as a replacement for potassium hydroxide. In addition, other chemicals such as
phosphoric acid and citric acid seem promising for use as modifiers for agricultural waste as they are less toxic.
Moreover, it was observed that the adsorption capacity of most of the chemically-modified agricultural wastes
was higher than that of the unmodified biomass owing to the increase in biomass active sites that chemical
modification provides. This present study provides perspectives on the understanding of the effects of chemical
modification of biomass, identification of knowledge gaps and directions for future research.

1. Introduction chemical precipitation, biological or electrochemical reduction, and

The past few years have seen a growing concern towards the non-
biodegradability of heavy metal ions in surface and groundwater
[1–3], particularly with industrialization and urbanization sitting at the
forefront in the depletion of water quality [4–8]. The carcinogenicity and
toxicity of some of these heavy metal ions have over the years informed
several research that seek to develop techniques for the removal of these
contaminants [9–15]. Factors such as poor recyclability, heightened cost,
convoluted method of adsorbent preparation, and removal capacity [14,
16,17] have often served as determiners for the sustainability and
acceptability of these techniques. The advent of techniques such as
membrane separation [5,16,18]. have been engaged in the removal of
contaminants from aqueous solution and there is a growing body of
literature that elevates the role and efficiency of adsorption due to its low
cost, adaptability, and environmental friendliness in the removal of
heavy metal ions from contaminated water bodies [5,16,19]. Adsorption
is a technique that involves the use of sorbent material to remove pol-
lutants such as metal-ions from loaded solution. Common adsorbents
such as activated charcoal, graphene, metal nanoparticles [16,20,21] are
actually expensive (thereby leading to an increased overall cost of the
removal process) and are limited by poor recyclability and low removal
capacity. In a conscious effort to overcome some of these shortcomings,

* Corresponding author.
E-mail addresses: ogunlaluoluwafemi@gmail.com (O. Ogunlalu), Ifeoluwapeter@gmail.com (I.P. Oyekunle), kingsleyiwuozor5@gmail.com (K.O. Iwuozor),
adaderibigbe@futa.edu.ng (A.D. Aderibigbe), emenikechizitere@gmail.com (E.C. Emenike).

https://doi.org/10.1016/j.crgsc.2021.100188
Received 23 June 2021; Received in revised form 4 October 2021; Accepted 9 October 2021
Available online 12 October 2021
2666-0865/© 2021 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-
nc-nd/4.0/).
O. Ogunlalu et al.
Xu, et al. [22] investigated the potential of polyacrylonitrile fibre as a
cheap and efficient adsorbent for the selective removal of mercury from
wastewater owing to its mechanical strength and large surface area. The
study reported that while the phosphorus-functionalized fibre demon-
strated heightened efficacy over a wide pH range (3–11) and achieved an
efficiency up to 99% in a ten-cycle period, there is still some complexity
in its preparation. Due to this, heightened efficiency may not be obtained
in a real-life scenario. Recently, researchers have shown an interest in the
search for novel materials that can perform at near-equal capacity to
activated carbon but at a cheaper cost. This led to the exploration of
various studies being carried out on lignocellulosic wastes [1], clay
substances [11,16], biochars [9,23], and a host of different biomasses.
Specifically, Xu, et al. [16] explored the potential of biochar prepared
from recycled waste art paper to serve as an adsorbent for Pb2þ from
wastewater. The results of their study revealed that biochar exhibited a
sorption capacity of 1555 mg/g for the removal of Pb(II) from waste-
water. Although this study presented a cheaper option and environ-
mentally friendly adsorbent, the non-reusability of the adsorbent was
limiting.
The use of agricultural wastes for adsorption however, is character-
ized with a number of constraints such as low metal removal efficiency,
limited surface area, fewer active sites for sorption and lesser surface
functional groups [24], hence the need for modification with other ma-
terials. Modification of biomass wastes for adsorption can be carried out
in several ways including chemical treatments, functionalization with
exogenous active functional groups, magnetization, doping with photo-
catalysts, and coupling with two or more adsorbents to form composite.
However, our interest is on the modification with chemicals. Though
many reviews have been published in this regard, the focus has always
been on more common substrates (such as banana peel [25–27],
cotton-based adsorbents [28–31]), a particular metal [32,33], orange
peel a broader scope that includes other modification techniques [34], or
simply have other interests like their sorption mechanisms and reuse
[24]. Nevertheless, very few has specifically focused on the effect of
chemical modification on several agricultural wastes adsorbents for the
uptake of various heavy metal ions. Therefore the aim of this paper is to
review the adsorptive performance of various unmodified and
chemically-modified agricultural wastes for the removal of different
heavy metals from aqueous solutions. This review will particularly help
in identifying knowledge gaps and provide further directions for future
research.
2. Overview of technologies used for remediation of heavy metal
ions
Physical separation methods like magnetic separation, electrostatic
separation, mechanical screening, and gravity concentration have been
employed, and many of these processes achieved separation based on
differences in size and shape of particles and other physically intrinsic
characteristics [6,35,36]. These studies have found applications mostly
in the removal of particulate metal or discrete particles. The efficiency of
these physical methods have also been reported to be hampered by
presence of clay or silt in contaminated water [36], and these limitations
have shifted focus to other methods.
As a result of its simplicity of operation, chemical precipitation is one
of the most widely employed methods of removing heavy metal ions
[36]. It involves the introduction of a chemical precipitant to react with
the heavy metal ions; hence resulting into metal precipitates that are
largely insoluble – which in turn can be filtered out. Common precipi-
tation methods include hydroxide precipitation and sulfite precipitation.
The former is very common due to its simplicity, low cost of operation
and the possibility of easy variation of pH [36,37]. Hydroxide precipi-
tation employs the use of Ca(OH)2 and NaOH and precipitation is usually
enhanced by the addition of coagulants such as alum and organic poly-
mers [38]. It is commonly used for the removal of Cu(II) and Cr(VI) while
sulfite precipitation on the other hand can be used for removing Cu(II),
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Current Research in Green and Sustainable Chemistry 4 (2021) 100188
Cd(II), and Pb(II) [36,37]. Sulfite precipitation produces precipitates
having lower solubilities than their hydroxide counterparts and as a
result a relatively larger amount of heavy metal ions can be remediated
using sulfite precipitation. However, chemical precipitation also suffers
from some limitations like heavy usage of chemicals which subsequently
generates excess sludge [37].
Ion exchange employs the use of resins which removes metals ions in
aqueous solution by replacement with sodium ion (Naþ). It is a non-
selective process that can be used for removal of a wide array of heavy
metal ions, and it is largely pH dependent. Synthetic organic ion-
exchange resins are the commonly-used exchangers, and this process is
largely efficient when used for low concentrated metal solutions [36].
Although, ion exchange allows for high transformation of components,
its disadvantage lies in the small amount of metal ions that it can reject
and the seemingly high cost of operation [37].
Filtration has also been in great use and sensitive filters are developed
based on the size of metal ions to be removed from the solution. Various
forms of filtration include membrane filtration, ultra-filtration, and
reverse osmosis [37]. Pores of ultra-filtration membranes are larger than
dissolved metal ions and as a result, polymers are used to overcome this
defect; thereby aiding removal of metal ions. Ultra-filtration has been
successfully employed to remove Cd(II) [39–41], Cu(II) [42–44], Ni(II)
[45–47], Pb(II) [48–50], and Zn(II) [51–53]. Moreover, reverse osmosis
involves passing wastewater through a semi-permeable membrane that
allows the rest of the water solution to pass through but retains the metal
ions to be removed [37]. Cu(II), Fe(II), Mn(II) and Ni(II) are amongst the
host of metal ions that can be removed through this process. Studies have
particularly shown that the little space requirement and heightened
removal capacity of filtration provide competitive advantages, however,
the associated complexity inherent in its application, high cost and
incessant cases of membrane fouling are notable demerits of this method
[37]. Filtration technique led to the introduction of forward osmosis for
remediation of heavy metals. This differs from reverse osmosis in that it is
driven by osmotic pressure gradient. It has also been reported to address
some limitations including membrane fouling, energy consumption, and
water recovery, associated with other filtration techniques [37,54].
Electrolytic recovery is one of the remediation techniques in which
the electricity is introduced into the metal-containing wastewater having
both the positive and negative electrode. This subsequently precipitates
the heavy metals in weak acid or neutralized catholyte as hydroxides
[36]. This technique presents heightened efficiency and low consump-
tion of chemicals, but the high energy requirement is a notable limitation
[37].
3. Adsorption as a remediation technique for heavy metal
mitigation
Different techniques have been utilized in remediation by various
authors based on their strengths and weaknesses. Some of the drawbacks
of the adsorption process include toxicity of wastes from spent adsor-
bents, the use of chemicals for desorption, and the transfer of the
pollution load rather than its elimination, however, some of its advan-
tages over other treatments include its flexibility and ease of operation
and design, low sludge volume and its low cost to set-up [55,56].
Different drawbacks peculiar to various remediation technologies have
led to the preference of adsorption for the removal of heavy metal ions
from aqueous systems. Methods like precipitation and coagulation are
known to consume a lot of chemicals and consequently produce very
toxic beds of sludge [37,57], and electrodialysis is associated with high
operating cost and corrosion [36,37]. This has often made adsorption a
key process for metal removal from wastewater [37]. The rate at which
heavy metal ions are taken up in an adsorption process is determined by
several factors such as pH, temperature, contact time, adsorbent dosage,
and nature of adsorbent. As a result of the extensive studies that have
been carried out on adsorption, different models have evolved over the
years which help researchers study the adsorption kinetics, adsorption
O. Ogunlalu et al.
isotherms and thermodynamic investigations of any sorption process.
There is also an advantage of adsorbent recovery associated with
adsorption, which is made possible through the desorption process [37].
In a research by Nitayaphat, Jintakosol [9], the potency of chito-
san/bamboo charcoal composite as an adsorbent was investigated for the
removal of Ag(I) from wastewater. The result of this study showed that at
a pH of 6, a maximum adsorption capacity was 52.91 mg/g. A further
probe into this study revealed that the adsorption capacity was also
largely influenced by the bamboo charcoal concentration. This may be
attributed to the large surface area and porosity of the bamboo charcoal
which has been conferred on the chitosan/bamboo charcoal composite.
This observation was also reinforced by the Scanning Electron Micro-
scope (SEM) image of the adsorbent which revealed a largely rough
surface with pores in contrast to the smooth surface observed when the
surface morphology of chitosan only was studied. The adsorption data
were also fitted to different kinetic models, and it was observed that the
best-fit equilibrium data was Langmuir. This suggests a mono-molecular
layer arrangement of adsorbate on the adsorbent surface. The desorption
study further revealed that Ag(I) can be adequately desorbed using
10 nM acetic acid and this suggests the reusability of the chito-
san/bamboo charcoal composite in addition to being biodegradable,
relatively cheap, and non-toxic.
Cekim et al. [58] also studied the efficacy of tobacco leaf for the
removal of Cu(II) from synthetic wastewater. They observed that the
adsorption of the Cu(II) was dependent on pH, temperature, adsorbent
dosage, and initial metal ion concentration. A further probe into the
study revealed that of the four isotherm models (Langmuir, Freundlich,
Temkin and Dubinin-Radushkevich isotherm) which the data were fitted
into, the adsorption data was best described by Langmuir isotherm with
an associated maximum adsorption capacity of 17.18 mg/g. In an
attempt to determine the extent of the adsorption of Cu(II) by the
adsorbent, the surface morphology of the tobacco leaf before and after
the biosorption was studied using SEM. The SEM image analysis conse-
quently revealed that a monolayer arrangement of metal ion was formed
on the available adsorption sites of the tobacco leaf.
In a research by Moyo et al. [59], the potential of Marula seed husk for
the adsorption of Pb(II) and Cu(II) from wastewater was investigated.
The efficiency of the adsorbent was studied in a batch adsorption system
and the result of the study showed that pH 5 and 6 were the most suitable
for maximum adsorption for Pb(II) and Cu(II)and the equilibrium
isotherm better fitted into the Langmuir isotherm model. The study
further reported an adsorption kinetics model that best fits the
pseudo-second order model which suggests the dependence of the
adsorption process on the amount of heavy metal ions in the solution and
available adsorption sites on the adsorbent.
Owing to the high cost associated with activated charcoal, Igwegbe,
et al. [15] in a recent study investigated the potential of using recycled
carbon materials from commercial supercapacitors as adsorbent for the
removal of Ag(I) and Cr(VI). They reported that the maximum adsorption
capacity of the two heavy metal ions was dependent on initial pH value
and adsorbent dosage. A maximum adsorption capacity on 104.0 mg/g
was observed for Ag(I). This value is significantly higher than the
adsorption capacities reported by Nitayaphat, Jintakosol [9]. This is
likely due the relatively lower surface area of the chitosan/bamboo
charcoal composite beads employed by Nitayaphat, Jintakosol [9].
Many studies have been focused on the search and development of
materials that have the capacity to adsorb heavy metal ions from solu-
tions onto their pores and adsorption active sites. Biomasses that have
been employed include agricultural materials like shells of wheat, orange
peels, sunflower leaves [1,61], biochars from plant residues, wood waste,
and manures. The high cost of commercial activated carbon has seen
biochar emerge as an alternative carbon-containing, easily accessible and
cost effective adsorbent with high degree of binding capacity. Biochar is
the residue produced upon pyrolysis of biomass (agricultural feedstock)
under limited supply of air [62,63]. The pyrolysis process is carried out to
procure the fluid products (liquid and gaseous species), hence the
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Current Research in Green and Sustainable Chemistry 4 (2021) 100188
produced char is considered a residue [64]. They have relatively struc-
tured carbon matrix, similar to activated carbon, with high degree of
porosity and surface area [65]. The physiochemical properties of a bio-
char such as composition, particle size and pore size distribution-which
determines its efficiency against a particular adsorbate, is largely
controlled by pyrolysis conditions and the feedstock characteristics [62].
Adsorption of heavy metals onto biomass surfaces can occur through
different mechanisms which includes intraparticle diffusion, hydrogen
bonding, electrostatic interaction, π-bonding, complexation, precipita-
tion and ion exchange [4,66]. A flowchart showing a representation of
the overall adsoption process using agricultural wastes is shown in Fig. 1.
4. Adsorption capacities of unmodified and chemically modified
agricultural waste adsorbents for heavy metal ion removal
Adsorption capacity is an intrinsic feature of an adsorbent which
determines its efficiency and effectiveness in removing a particular
adsorbate [4,67]. It is determined experimentally or theoretically using
isotherm models such as Langmuir, sips, Dubinin-Radushkevic, among
others [15]. The pH and temperature are important parameters in the
adsorption process. The pH influences metal speciation (a vital phe-
nomenon in the adsorption of metal on adsorbent surface), and dissoci-
ation of active functional sites of the sorbent [68]. Most metal adsorption
increases with pH up to a certain pH value and then decreases with
further pH increase [69]. Temperature influences the rate of reaction
between adsorbent and the adsorbate in aqueous system. Adsorbent
dosage is another important factor that influences adsorption process. it
determines the availability and ampleness of active sites on the adsorbent
for metal sorption [15]. An increase in adsorbent dosage increases the
availability of surface area or active sites in the adsorption capacity [70].
However, this increase in adsorbent dosage has also been reported to
decrease the amount of metal ion adsorbed [71–73]. This is attributed to
the higher adsorbent dose providing more active sites which resulted in
unsaturation of the sorption sites during the adsorption process [72,74,
75].
Due to its wide availability as forest industry waste, defatted Laurus
nobilis leaves was used by Gümüş [74] as a natural biosorbent for the
removal of toxic heavy metals such as Cd(II), Cu(II), Pb(II) and Zn(II)
from aqueous solution. The biosorption process was found to be tem-
perature and pH dependent, with a gradual increase in biosorption ca-
pacities as the pH increases. The process showed a maximum biosorption
capacities (qmax ) of 8.610, 6.040, 96.15 and 8.740 mg/g Cd, Cu, Pb and
Zn respectively. These results highlighted the effectiveness of Laurus
nobilis leaves for heavy metal remediation. Naseem et al. [76] studied
adsorption of Cu(II), Co(II) and Ni(II) ions from wastewater onto Vigna
radiata husk biomass under optimum conditions of adsorbent dosage,
contact time and pH of the medium. Maximum adsorption capacities for
Cu(II), Co(II) and Ni(II) ions were found to be 11.05, 15.04 and
19.88 mg/g respectively. The result revealed that the metal ions can
effectively be removed from aqueous medium by the plant husk. Rhizopus
oligosporous biomass produced from corn processing wastewater was
used as a biosorbent for the treatment of water synthetically contami-
nated with Hg(II) ions in a batch process experiment [77]. At pH 6 and
adsorbent dosage of 1 g/L, the adsorption capacity was found to be
33.33 mg/g, showing its potential to be used as an effective and eco-
nomic biosorbent material for Hg(II) removal. Similar results for the
removal of Hg(II) from wastewater were also obtained using other
agricultural wastes such as Pistachio hull waste [68], Barbula lambar-
enensis [78], ground bean husk [79], orange peel [80], among others.
Van Hien et al. [81] studied the remediation of zinc-contaminated
water using three different biomass residues (acacia wood chip, rice
husk and bamboo biochars). The mechanism of adsorption was found to
occur through intraparticle diffusion, complexation formation with
organic surface groups, ion exchange and precipitation with inorganic
groups. All three biochars effectively removed Zn(II) ions from the
aqueous solution, with bamboo biochar particularly more efficient with
O. Ogunlalu et al.
Fig. 1. Overall adsorption process using agricultural wastes (AW) [60].
removal efficiency up to 98%. The adsorption capacity for wood, rice
husk and bamboo biochars was respectively 4.02, 3.82 and 7.62 mg/g in
their own study, Rambabu, et al. [82] examined the biosorption of the
highly toxic hexavalent chromium ions (Cr6þ) from synthetic wastewater
onto date palm empty fruit bunch. A theoretical maximum adsorption
capacity of 70.49 mg/g was obtained for the biosorbent at an optimum
pH of 2 temperature of 30  C. This result demonstrated date palm empty
fruit bunch biowaste as an efficient, economic and environmentally
friendly biosorbent for sequestration of Cr(VI) ions from both domestic
and industrial wastewater streams. One of the highest adsorption ca-
pacities in literature for heavy metal uptake using an unmodified
low-cost agricultural waste was reported by Malik, Dahiya [83]. Using
coconut (Cocos nucifera L.) husk as adsorbent for the removal of Pb(II),
Cu(II), Ni(II) and Zn(II) ions, they experimentally obtained maximum
adsorption capacities of 362.2, 443, 404.5 and 388 mg/g respectively,
showing the high effectiveness of the coconut husk for heavy metals
uptake. A comprehensive summary on the removal of various heavy
metals using unmodified agricultural wastes is presented in Table 1.
Aside from the parameters presented in Table 1, other factors also
affect the uptake of heavy metals from solutions by agricultural wastes.
Initial metal ion concentration determines the amounts of metal ions
sorbed by an adsorbent. This is particularly important because a given
mass of the adsorbent can adsorb only a certain amount of metal ion [99].
Agitation speed provides the kinetic energy necessary to promote the
metal ions in overcoming mass transfer constraints at the solid-liquid film
[15,82]. Contact time influences the time taken by a metal ion and the
adsorbent to reach equilibrium. Normally, adsorption kinetics involves a
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Current Research in Green and Sustainable Chemistry 4 (2021) 100188
rapid initial stage followed by a much slower stage before attaining
equilibrium [72]. The particle size of the adsorbent determines the sur-
face area through which the mass transfer is carried out, from liquid
phase to solid phase. Small particle size implies higher surface area, and
hence, more pores per unit available for uptake of the heavy metal ions
[146].
Drawbacks experienced in the adsorption capacities of selected ad-
sorbents have led to studies that are addressing ways to overcome or
potentially-increase them. Recent works have focused on the effects of
chemical modification of agricultural wastes on the adsorption efficiency
of heavy metal ions from a loaded system. In this process, the natural
form of the waste is impregnated into selected chemicals until it assumes
enough capability to increase adsorption efficiency. The addition of
active sites which is influenced by the chemical modification process
have been investigated and confirmed by Infra-Red spectra and Scanning
Electron Microscopy images. A vast array of modifying agents have been
employed over time and they include NaOH [147], citric acid [124],
epichlorohydrin [148], ammonium citrate [149], among others. Table 2
compares the adsorption capacities of certain adsorbents before and after
modification and shows how in most cases chemical modification helps
to increase sorption of heavy metal ions.
5. Equilibrium isotherm and kinetics modelling
The role played by equilibrium adsorption isotherm and kinetics
modelling in the describing the interaction between the adsorbent and
adsorbate cannot be discounted. At a constant temperature under the
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

Table 1
Adsorption capacities of some unmodified adsorbents.
Adsorbent Maximum capacity (mg/g) Dosage (g/L) Temp. ( C) pH Qmax determination method Refs

Cd(II)
Laurus nobilis leaves 8.610 2.0 – 6.5 Langmuir [74]
Neem leaf powder 250.0 - - 9.5 Langmuir [84]
Litchi peel 230.5 1.0 25 5.0 Langmuir [85]
Orange peel 170.3 1.0 25 5.0 Langmuir [85]
Pomegranate peel 132.5 1.0 25 5.0 Langmuir [85]
Banana peel 98.40 1.0 25 5.0 Langmuir [85]
Sesame leaf and stem 84.74 50 – 6.0 Langmuir [86]
Ulmus carpinifolia leaves 83.30 - - 3.5 Langmuir [87]
Fraxinus excelsior leaves 73.53 - - 4.0 Langmuir [87]
Teucrium herb 56.82 5.0 - - Langmuir [70]
Equisetum herb 52.91 5.0 - - Langmuir [70]
Biochar from diary manure 51.40 - - - Langmuir [23]
Boiler fly ash 49.67 – - - Experiments [88]
Psidium guajava peel 39.68 - - 7.0 Langmuir [89]
Carnauba fruit exocarp 58.00 – 28 5.0 Langmuir [90]
Peanut husk biochar 28.99 40 23 5.0 Langmuir [91]
Ficus religiosa leaf powder 27.14 – 50 4.0 Langmuir [92]
Parkia spaciosa pods 25.64 - - 7.0 Langmuir [89]
Biochar from diary manure 23.64 - - 5.0 Langmuir [85]
Sugarcane bagasse 19.49 – – 5.5 Langmuir [93]
Dry persimmon leaves 18.26 3.0 25 6.0 Langmuir [94]
Ananas comosus peel 18.21 - - 7.0 Langmuir [89]
Activated carbon 8.000 10 25 5.0 Langmuir [95]
Oak bark char 5.400 10 25 5.0 Langmuir [95]
Cabbage leaves powder 4.840 10 – 6.0 Langmuir [96]
Bagasse fly ash 1.240 10 50 6.0 Langmuir [97]
Pine wood char 0.370 10 25 5.0 Langmuir [95]
Pine bark char 0.340 10 25 5.0 Langmuir [95]
Cu(II)
Laurus nobilis leaves 6.040 2.0 – 6.0 Langmuir [74]
Vigna radiata husk 11.05 1.0 25 5.0 Langmuir [76]
Coconut husk 443.0 0.5 30 6.0 Langmuir [83]
Green coconut shell powder 285.7 - 27 7.0 Langmuir [98]
Ulmus carpinifolia leaves 76.30 – – 3.5 Langmuir [87]
Orange peel 63.30 1.0 20 5.0 Langmuir [99]
Activated carbon derived from Gliricidia sipium leaf 61.66 - – 8.0 Langmuir [100]
Spartina alterniflora derived biochar 48.49 - 25 6.0 Langmuir [101]
Paper mulberry leaf powder 43.40 – 35 6.0 Langmuir [102]
Activated carbon derived from Mudra leaf 35.71 - – 7.0 Langmuir [100]
Fraxinus excelsior leaves 33.44 – – 4.5 Langmuir [87]
Activated carbon derived from Nirgudi leaf 29.41 - – 7.0 Langmuir [100]
Date seed derived biochar 26.75 5.0 20 6.0 Sips [103]
Dry persimmon leaves 19.42 3.0 25 6.0 Langmuir [94]
Wheat shells 17.42 20 60 6.0 Langmuir [104]
Tobacco leaves 17.18 0.4 – 4.0 Langmuir [58]
Peanut hulls 14.13 20 25 4.0 Langmuir [105]
Corn straw biochar 12.52 1.0 – 5.0 Langmuir [106]
Peanut husk 11.36 - 25 6.0 Langmuir [107]
Marula seed husk 10.20 10 20 6.0 Langmuir [59]
Lentil shells 9.590 0.5 60 5.0 Langmuir [104]
Pinus halepensis sawdust 9.590 10 – 7.0 Langmuir [69]
Rubber leaf powder 8.920 1.0 – 4.5 Langmuir [108]
Hardwood biochar 6.790 1.0 – 5.0 Langmuir [106]
Cabbage leaves powder 5.750 10 – 6.0 Langmuir [96]
Rice shells 2.950 1.0 60 5.9 Langmuir [104]
Rice husk 2.480 0.8 - - Langmuir [108]
Cocoa pod husk 2.009 – - - Langmuir [109]
Pomegranate peel 1.320 – – 5.8 Langmuir [110]
Pomegranate peel 1.318 50 5.8 Langmuir [111]
Ni(II)
Coconut husk 404.5 10 30 6.0 Experiment [83]
Vigna radiata husk 19.88 1.4 25 8.0 Langmuir [76]
Activated carbon 133.0 – – 6.0 Langmuir [112]
Litchi chinensis seed 66.20 1.0 25 7.5 Langmuir [113]
Peanut husk 56.82 5.0 25 6.0 Langmuir [107]
Citrus limettioides peel 38.46 1.5 27 6.0 Langmuir [114]
Seed carbon 35.54 1.5 27 6.0 Langmuir [114]
Moringa olifera bark 26.84 0.4 30 6.0 Langmuir [115]
Banana peels 26.10 0.1 76 6.0 Langmuir [116]
Mucor hiemalis biomass 21.32 0.5 40 8.0 Langmuir [117]
Date seed derived biochar 19.54 10 20 6.0 Sips [103]
Cashew nutshell 18.86 3.0 30 5.0 Langmuir [1]
Tea factory waste 15.26 10 60 4.0 Langmuir [118]
(continued on next page)

5
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

Table 1 (continued )
Adsorbent Maximum capacity (mg/g) Dosage (g/L) Temp. ( C) pH Qmax determination method Refs

Lansium domesticum peel 10.10 6.0 30 – Langmuir [119]

Barley straw ash 8.250 – 25 6.5 Langmuir [120]
Sugarcane bagasse 2.000 10 25 5.0 Experimental [121]
Bagasse fly ash 1.700 10 50 – Langmuir [97]
Brassica campestris stem 1.100 20 20 9.0 Langmuir [122]
Pb(II)
Coconut husk 362.2 10 30 5.0 Experiment [83]
Activated carbon 129.8 – – 5.0 Langmuir [112]
Brassica campestris stem 78.00 1.0 60 4.0 Langmuir [122]
Solanum melongena leaf 71.42 0.4 50 5.0 Langmuir [123]
Biochar from diary manure 50.41 – – 9.5 Langmuir [85]
Plantain peels 47.62 – 55 5.0 Langmuir [124]
Peanut shell 39.00 2.0 20 5.5 Langmuir [125]
Carnauba fruit exocarp 33.00 – 28 5.0 Langmuir [90]
Sugarcane bagasse 31.45 – – 5.5 Langmuir [93]
Peanut husk 27.03 5.0 25 6.0 Langmuir [107]
Coconut shell carbon 26.50 – – 4.5 Langmuir [126]
Coffee pulp 24.10 – 20 2.0 Langmuir [127]
Marula seed husk 20.00 0.8 20 5.0 Langmuir [59]
Dry persimmon leaves 22.59 3.0 25 6.0 Langmuir [94]
Sweet potato peels 18.00 – 25 7.0 Langmuir [128]
Pinus halepensis sawdust 13.48 10 – 5.0 Langmuir [69]
Oak bark char 13.11 10 25 5.0 Langmuir [95]
Pine wood char 4.120 10 25 5.0 Langmuir [95]
Pine bark char 3.000 10 25 5.0 Langmuir [95]
Oak wood char 2.560 10 25 5.0 Langmuir [95]
Laurus nobilis leaves 96.15 2.0 – 6.0 Langmuir [74]
Cr(VI)
Date palm empty fruit bunch 70.49 – 30 4.0 Langmuir [82]
Heinsia crinita seed coat 231.7 5.0 55 2.0 Langmuir [129]
Foxtail millet shell 11.70 4.0 25 5.0 Langmuir [130]
Apricot kernel shell 6.500 3.0 35 3.0 [131]
Activated carbon from orange peel 22.73 5.0 30 2.5 Langmuir [132]
Brassica campestris stem 3.900 – 20 9.0 Langmuir [122]
Zn(II)
Laurus nobilis leaves 8.340 2.0 – 6.0 Langmuir [74]
Urtica dioica leaves 1.039 20 25 4.0 Langmuir [133]
Rice husk 19.62 – 25 7.0 Langmuir [134]
Artocarpus altilis seed husk 90.91 5.0 27 6.0 Langmuir [72]
Groundnut shell 7.620 – – 5.9 Langmuir [135]
Saw dust 10.96 – – 5.9 Langmuir [135]
Jute fibers 3.550 – – 5.9 Langmuir [136]
Wood biochar 4.020 13 25 5.5 Langmuir [81]
Rice husk biochar 3.820 13 25 5.5 Langmuir [81]
Bamboo biochar 7.620 13 25 5.5 Langmuir [81]
Coconut husk 338.0 10 30 7.0 Langmuir [83]
Hg(II)
Barbula lambarenensis 4.740 – 40 5.5 Langmuir [78]
Pistachio hull waste 48.78 1.0 30 7.0 Experiment [68]
Rhizopus oligosporous biomass 33.33 1.0 30 6.0 Langmuir [77]
Ground bean husk 2.309 – – 6.0 Dubinin-Radushkevic [79]
Rambail leaves 122.0 2.0 30 4.0 Langmuir [71]
Orange peel 7.462 – 25 4.0 Langmuir [80]
As(III)
Activated carbon from dialium guineense 48.08 4.0 30 6.0 Langmuir [137]
Acacia nilotica stem 53.60 4.0 25 7.5 Langmuir [138]
Moringa oleifera seed 1.590 – – 7.5 Langmuir [139]
Rice polish 0.139 20 20 7.0 Langmuir [140]
As(V)
Moringa oleifera seed 2.160 – – 2.5 Langmuir [139]
Rice polish 0.147 20 20 4.0 Langmuir [140]
Co(II)
Vigna radiata husk 15.04 1.2 25 5.0 Langmuir [76]
Artocarpus altilis seed husk 100.0 5.0 27 6.0 Langmuir [72]
Barley straw ash 5.580 – 25 6.5 Langmuir [141]
Teucrium herb 39.06 5.0 25 – Langmuir [70]
Equisetum herb 40.82 5.0 25 – Langmuir [70]
Black carrot residues 6.309 – 60 5.3 Langmuir [142]
Fe(II)
Cocoa pod husk 4.160 10 – 7.5 Langmuir [143]
Rice husk ash 66.66 5.0 30 5.0 Langmuir [144]
Mn(II)
Rice husk ash 3.170 5.0 30 5.0 Langmuir [144]
Black carrot residues 5.170 – 60 5.3 Langmuir [142]
White rice husk ash 18.01 2.5 35 7.0 Langmuir [145]

6
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

Table 2
Comparison of the adsorption capacities of modified and unmodified adsorbents.
Adsorbent Metal ion Modifying agent Adsorption capacities (mg/g) References

Original Modified
Form Form

Oiltea camellia shell Cd(II) Sodium silicate 62.18 211.5 [150]

Chitosan-alginate beads Pb(II) Epichlorohydrin triphosphate 60.27 166.9 [151]
Chitosan-alginate beads Pb(II) Tetraethylene pentaamine 60.27 259.6 [152]
Chitosan (sand) Pb(II) EGTA 12.38 103.6 [152]
Polyaniline 12.38 16.07
Magnetite 12.38 63.33
TiO2 nanoparticles Cd(II) Humic acid 15.20 9.900 [2]
Extractant of walnut shell 15.20 25.70
1,5-diphenyl carbazon 15.20 31.70
Litchi pericarp Cu(II) NaOH 8.830 23.70 [111]
Chitosan beads Cu(II) Carboxy methyl 53.20 130.23 [153]
Chitosan (sand) Cu(II) Tripolyphosphate 8.180 26.06 [153]
ECH 8.180 35.46
Poplar Sawdust Cu(II) NaOH 3.970 8.200 [154]
Poplar Sawdust Cu(II) KOH 3.970 7.860 [154]
Cherry Sawdust Cu(II) NaOH 2.080 7.380 [154]
Cherry Sawdust Cu(II) KOH 2.080 11.06 [154]
Spruce Sawdust Cu(II) NaOH 2.130 9.020 [154]
Spruce Sawdust Cu(II) KOH 2.130 10.52 [154]
Hornbeam Sawdust Cu(II) NaOH 4.320 7.710 [154]
Hornbeam Sawdust Cu(II) KOH 4.320 9.490 [154]
Sugarcane Bagasse Cu(II) Citric acid 4.840 5.350 [155]
Rice Husk Pb(II) KMnO4 14.70 86.50 [156]
Corn cob Cd(II) KMnO4 þ acrylamide þ N,N-methylenebisacrylamide þ Conc. H2SO4 4.960 18.35 [157]
Barley Straw Cu(II) Citric Acid 4.640 31.71 [158]
Litchi pericarp Cu(II) NaOH 8.830 23.70 [159]
Barbula lambarenensis Pb(II) Sodium tripolyphosphate 90.00 143.0 [160]
Barbula lambarenensis Pb(II) Ethylene glycol 90.00 100.0 [160]
Avocado seed Pb(II) Phosphoric acid 18.90 26.60 [161]
Acorus calamus rhizome Pb(II) HCl 72.43 76.09 [162]
Acorus calamus rhizome Pb(II) NaOH 72.43 85.50 [162]
Black cumin seeds Cd(II) KMnO4 18.16 23.87 [163]
Black cumin seeds Cd(II) H3PO4 18.16 19.48 [163]
Barbula lambarenensis Cd(II) Sodium tripolyphosphate 50.00 52.60 [160]
Barbula lambarenensis Cd(II) Ethylene glycol 50.00 58.80 [160]
Black cumin seeds Cr(VI) KMnO4 15.81 16.06 [163]
Black cumin seeds Cr(VI) H3PO4 15.81 17.25 [163]
Citrus limettiodes peel Cr(VI) Sulphuric acid 99.50 176.5 [164]
Orange peel Cr(VI) CaCl2 12.29 4.950 [165]
Cassava peel Cr(VI) Citric acid 6.830 7.920 [146]
Lemon peel Cr(VI) Citric acid 5.920 8.660 [146]
Avocado seed Cr(VI) Phosphoric acid 3.390 5.100 [161]
Acorus calamus rhizome Cr(VI) HCl 15.31 23.86 [162]
Acorus calamus rhizome Cr(VI) NaOH 15.31 25.50 [162]
Harpagophytum procumbens roots Cr(VI) HCl 77.24 99.24 [66]
Peanut hull powder Hg(II) Mercaptoacetic acid 30.30 83.30 [166]
Cajanus cajan husk Hg(II) Ethanol þ NaOH þ CaCl2 45.80 67.15 [167]
Black cumin seeds Co(II) HCl 28.05 78.58 [168]
Black cumin seeds Co(II) NaOH 28.05 87.54 [168]
Jujube seeds Zn(II) H2SO4 16.72 221.1 [169]
Black cumin seeds Ni(II) HCl 28.55 90.41 [168]
Black cumin seeds Ni(II) NaOH 28.55 95.59 [168]
Orange peel As(VI) H2SO4 86.95 98.03 [170]
Banana peel Mn(II) HCl 2.864 4.736 [171]
Banana peel Mn(II) NaOH 2.864 3.601 [171]

equilibrium condition, the relationship between the amount of adsorbate
that is adsorbed to the surface of an adsorbent and the concentration of
adsorbate in the solution is referred to as adsorption isotherm [172]. The
kinetics shows the adsorption rate constants and is determined based on
the uptake amount per time [173]. The modelling of the adsorption data
into equilibrium isotherms and kinetics expressions is one of the most
important aspects of adsorption studies as they throw more light on the
on the interaction between the adsorbate and adsorbent through the
distribution of the adsorbate between the solid and liquid phases at
equilibrium and also assist in the replication of the process especially at
Industrial scale [174,175]. The most utilized method to determine the
kinetic model that best explains the adsorption is the linear least squares
(linear regression) which relates that the closer the determination
co-efficient is to unity (1), the more it is likely to be a good fit to explain
the experimental adsorption process. Although this method may be
affected by normality assumptions of the standard least squares and the
error variance [176], it was still the most utilized method for kinetic
modelling using the chemically modified bio sorbents as shown in
Table 3. Various models have been employed for investigating the
equilibrium isotherm and adsorption kinetics of heavy metal ions from
aqueous systems. An empirical study of a few of these models is given
below. As evident from Table 3, the most reported equilibrium isotherm
utilized for the mitigation of heavy metal ions include Langmuir
isotherm, Freundlich isotherm.
Langmuir isotherm defines a mono-molecular layer arrangement of
adsorbate on the surface of the adsorbent and suggests no interaction

7
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

Table 3
Best fit Isotherm and Kinetic Models for Heavy Metal Ions Adsorption.
Adsorbent Modifying agent Best-fit Isotherm R2 Best-fit Kinetics R2 Refs

Cd(II)
Pineapple leaf EDTA Langmuir 0.9909 Pseudo-second 0.9967 [182]
order
NaOH and Isopropyl alcohol Langmuir 0.9746 Pseudo-first order 0.9982
Oiltea camellia shell Sodium silicate Langmuir 0.9922 – – [150]
Punnai shells H2SO4 Freundlich 0.9966 Pseudo-second 0.9907 [183]
order
Camphor leaves NaOH þ Succinic anhydride þ NaHCO3 Langmuir 0.9909 Pseudo-second 1.0000 [184]
order
Palm Kernel Shells H3PO4 Freundlich 0.9999 Pseudo-first order 0.9985 [185]
Corn cob KMnO4 þ acrylamide þ N,N-methylenebisacrylamide þ Conc. Langmuir 0.9973 Pseudo-second 0.9990 [157]
H2SO4 order
Kush grass NaOH Langmuir 0.9970 Pseudo-second 0.9970 [186]
order
Bamboo leaves NaOH Langmuir 0.9870 Pseudo-second 0.9910 [186]
order
Moringa oleifera leaves powder NaOH þ Citric acid Langmuir – Pseudo-second 0.9666 [115]
order
Black cumin seeds (Nigella KMnO4 Langmuir 0.9980 Pseudo-second 0.9987 [163]
sativa) order
Black cumin seeds (Nigella H3PO4 Freundlich 0.9921 Pseudo-second 0.9973 [163]
sativa) order
Barbula lambarenensis Sodium tripolyphosphate Freundlich 1.0000 Pseudo-second 1.0000 [160]
order
Barbula lambarenensis Ethylene glycol Freundlich 0.9900 Pseudo-second 0.9800 [160]
order
Cu(II)
Eucalyptus wood H2O2 Langmuir 0.9976 – – [187]
Orange peels Polyethylene glycol Freundlich 0.9995 – – [188]
Pomegranate peels Polyethylene glycol Freundlich 0.9904 – – [188]
Punnai shells H2SO4 Freundlich 0.9684 Pseudo-second 0.9923 [183]
order
Rice straw Hydrated titanium oxide Langmuir 0.988 Pseudo-second 0.9900 [189]
order
Camphor leaves NaOH þ succinic anhydride þ NaHCO3 Langmuir 0.9848 Pseudo-second 0.9999 [184]
order
Chickpea husk KOH þ K2CO3 Freundlich 0.9970 Pseudo-first order 0.9989 [190]
Peanut husk Fe3O4 þ iminodiacetic acid Langmuir 0.9660 Elovich 0.9840 [181]
Sugarcane bagasse CH3COOH þ H2O2 Freundlich 0.9853 – – [191]
Sugarcane straw CH3COOH þ H2O2 Freundlich 0.9911 – – [191]
Litchi pericarp NaOH Langmuir 0.9916 Pseudo-second 1.0000 [159]
order
Moringa oleifera leaves powder NaOH þ citric acid Langmuir – Pseudo-second 0.9531 [115]
order
Loquat leaves NaOH Langmuir 0.9994 Pseudo-second 0.9995 [192]
order
Ni(II)
Punnai shells H2SO4 Freundlich 0.9791 Pseudo-second 0.9923 [183]
order
Camphor leaves NaOH þ succinic anhydride þ NaHCO3 Langmuir 0.9993 Pseudo-second 1.0000 [184]
order
Rice straw Epichlorohydrin þ N,N-dimethylenetriamine þ triethylamine Langmuir 0.9981 Pseudo-second – [193]
order
Mangosteen shell H2SO4 Langmuir 0.9990 – – [194]
Moringa oleifera leaves powder NaOH þ citric acid Langmuir Pseudo-second 0.9189 [115]
order
Rapeseed oil cake Na2CO3 Langmuir 0.9702 Pseudo-second 0.9982 [112]
order
Pb(II)
Lotus seed pods 2,2,6,6-tetramethylpiperidine-1-oxy Langmuir 0.9986 Pseudo-second 1.0000 [195]
order
Pineapple leaf EDTA Langmuir 0.9976 Pseudo-second 0.9956 [182]
order
NaOH and isopropyl alcohol Langmuir 0.9775 Pseudo-first order 0.9982 [182]
Chickpea husk KOH þ K2CO3 Freundlich 0.9687 Pseudo-first order 0.9970 [190]
Palm kernel shells H3PO4 Freundlich 0.9993 Pseudo-first order 0.9986 [185]
Acacia arabica seeds KOH Langmuir 0.9984 Pseudo-second 0.9990 [196]
order
Peanut husk Fe3O4 þ Iminodiacetic acid Langmuir 0.9910 Elovich 0.9780 [181]
Rapeseed oil cake Na2CO3 Langmuir 0.9921 Pseudo-second 0.9992 [112]
order
Loquat leaves NaOH Langmuir 0.9993 Pseudo-second 0.9997 [192]
order
(continued on next page)

8
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

Table 3 (continued )
Adsorbent Modifying agent Best-fit Isotherm R2 Best-fit Kinetics R2 Refs

Prunus dulcis seed shell powder Na2HPO4 Freundlich 0.9920 Pseudo-second 0.975 [197]
order
Barbula lambarenensis Sodium tripolyphosphate Langmuir 1.0000 Intraparticle 0.9700 [160]
diffusion
Barbula lambarenensis Ethylene glycol Langmuir 1.0000 Pseudo-second 1.0000 [160]
order
Avocado seed Phosphoric acid Freundlich 0.9120 Pseudo-second 0.9890 [161]
order
Cr(VI)
Black cumin seeds (Nigella KMnO4 Langmuir 0.9956 Pseudo-second 0.9974 [163]
sativa) order
Black cumin seeds (Nigella H3PO4 Langmuir 0.9987 Pseudo-second 0.9912 [163]
sativa) order
Citrus limettioides peel Sulphuric acid Langmuir 0.9990 Pseudo-second 0.9990 [164]
order
Avocado seed Phosphoric acid Langmuir 0.9120 Pseudo-first order 0.9910 [161]
Hg(II)
Peanut hull powder Mercapto acetic acid Langmuir 0.9900 Pseudo-second 0.9980 [166]
order
Cajanus cajan husk Ethanol þ NaOH þ CaCl2 Langmuir 0.9889 Pseudo-second 0.9935 [167]
order
As(III)
AC from Dialium guineense seed ZnCL2 Freundlich 0.9980 – – [137]
shell
Fe(III)
Orange peel Formaldehyde Langmuir 0.9007 Pseudo-second 0.9891 [198]
order
Green tomato husk Formaldehyde Langmuir- 0.9890 Pseudo-second 0.9980 [199]
Freundlich order
Mn(II)
Green tomato husk Formaldehyde Freundlich 0.9750 Pseudo-second 0.9990 [199]
order

between the adsorbed molecules [177,178]. The non-linear and linear which may include mass transfer or/and chemical reactions [180]. The
forms are shown in Equations (1) and (2) respectively: adsorption kinetics may be influenced by intra-particle precipitation,
complexation reaction, transfer of the heavy metals to the surface of the
qm KL Ce various adsorbents, movement, and retention of the heavy metals to the
qe ¼ (1)
1 þ KL Ce intra-particle active sites from the surface of the various adsorbents. As
  evident from Table 3, the most reported kinetic models utilized for the
1 1 1 1 mitigation of heavy metal ions include the Pseudo-firstorder and
¼ þ (2)
qe KL qm Ce qm Pseudo-second order models.
Pseudo-first-order model assumes that the amount of heavy metal
where qe is the amount of pollutant adsorbed per unit mass at equilibrium ions that are adsorbed by an adsorbent is directly proportional to the
(mg/g); qm is the maximum adsorbate that can be adsorbed per unit mass difference in concentration saturation level. Mathematically, the non-
of adsorbent (mg/g); KL is the adsorption equilibrium constant, and Ce is linear and linear forms of the model are represented by equations (5)
the concentration of adsorbent (mg/L). To obtain a suitable graph, a plot and (6) respectively:
of 1/qe against 1/Ce was made to yield values for the constants.
On the other hand, Freundlich isotherm model suggests that dqt
¼ k₁ðqe  qt Þ (5)
adsorption occurs in form of a mono-molecular layer or multilayer on dt
heterogeneous adsorbent surfaces and that there is an interaction be-
 
tween the adsorbed molecules [179]. The non-linear and linear forms of k1
logðqe  qt Þ ¼ log qe  t (6)
the isotherm are mathematically represented by Equations (3) and (4) 2:303
respectively:
where: k1 (min1) is the rate constant of the pseudo-first-order reaction;
qe ¼ KF Ce1=n (3) qe and qt denote the amount adsorbed onto the adsorbent (mg g1) at a
specific time, t (mins) respectively.
1 The pseudo-second order-model suggests that the adsorption of heavy
log qe ¼ log KF þ log Ce (4)
n metal ions is contingent on the number of pollutant ions in the solution
and the available adsorbent adsorption sites [179]. Equations (7) and (8)
where Ce (mg/L) and qe (mg/g) are the equilibrium concentration of
show the non-linear and linear forms of the model respectively:
adsorbent in the solution and the amount of adsorbate adsorbed at
equilibrium respectively; n represents adsorption intensity and KF (mg1-1/ dqt
n 1/n 1 ¼ k₂ðqe  qt Þ2 (7)
L g ) denotes the adsorption capacity for the adsorbent. The values dt
of the constants were obtained by plotting log qe against log Ce. Table 3
reveals that the metal ion adsorption was best fit to either Langmuir or t 1 1
¼ þ t (8)
Freundlich isotherm model. This suggests that the adsorption of the qt k2 q2e qe
heavy metal ions may occur as monolayer onto the active sites of the
adsorbent or as multilayers on the heterogenous surface of the adsorbent. where: k2 (g mg1 min1) is the rate constant of the pseudo-second-order
The kinetic models are used to study the adsorption mechanism reaction; qe denotes the adsorption amount (mg g1) and qt represents

9
O. Ogunlalu et al.
adsorption amount at a specific time, t (min). Elovich Kinetic model has
been applied for kinetic studies of Cu(II) in heterogeneous systems. The
non-linear and linear forms represented mathematically by Equations (9)
and (10) respectively:
qt ¼ β lnðαβtÞ (9)
1 1
qt ¼ lnðαβÞ þ lnðtÞ (10)
β β
where: qt ((mg/g) is the quantity of adsorbate adsorbed at time, t (min); α
is a constant related to chemisorption rate and β is a constant that shows
extent of surface coverage.
It is obvious that the sorption of the metal ions majorly conforms to
the pseudo-second order kinetics, although a few deviations such as
pseudo-first order and elovich kinetic model was reported for modified
peanut husk [181]. These suggest that the adsorption of the metal ion
depends on the amount present in the effluent and the available
adsorption sites on the adsorbent. Additionally, it implies that the
chemisorption reaction between the heavy metal ions and the various
functional groups on the chemically modified adsorbents is through
electron exchange as shown in Fig. 2 [176,180].
6. Thermodynamics modelling
For the successful modelling of any thermodynamic study, key terms
such as Gibb's free energy, enthalpy, and entropy must be engaged, and
deductions made. In determining the enthalpy, entropy and the Gibb's
free energy, Equations 17–19 are usually employed:
ΔG ¼ ΔH  TΔS (17)
Fig. 2. Mechanism of heavy metal adsorption on the surface of adsorbent [60].
10
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
ΔS ΔH
Ln K ¼  (18)
R RT
ΔG ¼  RT LnK (19)
where K is the adsorption equilibrium constant. ΔS, ΔG and ΔH represent
the entropy changes (JK1mol1), Gibbs energy (KJ mol1) and enthalpy
(KJ mol1). Temperature is represented with T (Kelvin) and R stands for
the molar gas constant (J mol1K1). The enthalpy describes the
response of thermal energy change that the system undergoes [200]. This
change could be an increase or a decrease in temperature. The enthalpy
could either have a positive or negative value as seen in Table 3. A
negative value of ΔH shows that the reaction is exothermic and the
adsorption of the heavy metals would be favoured by a decrease in
temperature of the system while a positive value shows that the reaction
is endothermic and the adsorption process would be favoured by an in-
crease in temperature [201]. For industrial scale-up of the adsorption
process, an increase in temperature equated to an increase in the cost of
treatment and should be highly avoided. The Gibb's free energy on the
other hand tells us the possibility of an adsorption process occurring. A
negative value of ΔG tells that the reaction is favourable or spontaneous
while a positive value explains that the reaction is rather unfavourable.
From Equation (17), it can be deduced that the spontaneity of an
adsorption process is favoured by either ΔH ˂ 0, or ΔS ˃ 0. Finally, the
entropy is the degree of disorderliness of a system. The adsorption pro-
cess is favoured when there is constant association or interaction be-
tween the heavy metals and the agricultural wastes prior to equilibrium.
This increase in disorderliness in the solid-solution interface at high
entropy favours the adsorption process [202].
Table 4 contains the summary of thermodynamics studies conducted
by various authors. Kong et al. [159] utilized Litchi pericarp in the
O. Ogunlalu et al. Current Research in Green and Sustainable Chemistry 4 (2021) 100188

adsorption of Cu(II) and the results obtained show that at the same
temperature, the reaction was favourable (-ve ΔG) using the modified
adsorbent while it was unfavourable with the unmodified adsorbent. This
shows that the chemical modification and adsorbent type play key role in
the energy configuration of the adsorption process. Therefore, for suc-
cessful industrial scale-up of the adsorption process utilizing minimal
energy, ΔH ¼ -ve, ΔG ¼ -ve, and ΔS ¼ þve, and these conditions are
observed in eucalyptus wood/H2O2 [187] for Cu(II) adsorption, Lansium
domesticum peel [119], and sugarcane bagasse [121] for Ni(II) uptake.
7. Chemical modification of agricultural wastes
Chemical activation involves the impregnation of agricultural wastes
with acidic, basic or neutral chemicals before or after carbonization at a

Table 4
Thermodynamics of metal ion uptake onto modified and unmodified adsorbents.
Adsorbent Modifying Agent Thermodynamic Parameter Refs

Temp ΔG (KJ/ ΔH (KJ/ ΔS (J/mol/

(K) mol) mol) K)

Cd(II)
Punnai shells H2SO4 298 0.360 232.8 0.720 [183]
Camphor leaves NaOH þ Succinic anhydride þ NaHCO3 303 17.36 19.21 6.272 [184]
Sugarcane bagasse Mercerizing agent þ succinic anhydride þ acetic anhydride – 26.08 – – [203]
Corn cob KMnO4 þ acrylamide þ N,N-methylenebisacrylamide þ Conc. 303 11.47 0.719 0.040 [157]
H2SO4
Kush grass NaOH 308 1.506 5.500 1.580 [186]
Sugarcane bagasse Mercerizing agent þ succinic anhydride þ 1,3-diisopropyl – 27.04 – – [203]
carbodiimide
Bamboo leaves NaOH 308 1.731 9.283 2.673 [186]
Moringa oleifera leaves powder NaOH þ Citric acid 303 4.500 15.27 62.57 [115]
Cu(II)
Chickpea husk KOH þ K2CO3 303 19.82 8.531 93.14 [190]
Eucalyptus wood H2O2 298 111.8 54.98 0.191 [187]
Punnai shells H2SO4 298 3.307 392.1 1.167 [183]
Sugarcane Bagasse Mercerizing agent þ succinic anhydride þ acetic anhydride – 24.25 – – [203]
Rice straw Hydrated Titanium oxide 298 0.579 25.35 0.087 [189]
Camphor leaves NaOH þ Succinic anhydride þ NaHCO3 303 7.768 22.92 5.340 [184]
Sugarcane Bagasse Mercerizing agent þ succinic anhydride þ 1,3-diisopropyl – 28.22 – – [203]
carbodiimide
Marula seed husk – 293 4.840 44.70 0.170 [59]
Peanut Husk Fe3O4 þ Iminodiacetic acid 298 1.400 23.00 0.080 [181]
Litchi pericarp – 298 5.090 3.500 0.030 [159]
Litchi pericarp NaOH 298 2.740 21.09 0.060 [159]
Moringa oleifera leaves powder NaOH þ Citric acid 303 3.750 12.76 52.60 [115]
Sugarcane Bagasse Citric acid – 6.340 11.82 60.94 [204]
Barley straw ash – 298 52.78 0.055 0.177 [120]
Ni(II)
Punnai shells H2SO4 298 1.179 523.7 1.539 [183]
Lansium domesticum peel – 303 17.50 16.50 0.003 [119]
Camphor leaves NaOH þ Succinic anhydride þ NaHCO3 303 10.62 31.27 67.92 [184]
Sugarcane bagasse – 298 20.78 74.32 332.3 [121]
Rice straw Epichlorohydrin þ N,N-dimethylenetriamine þ triethylamine 298 0.945 9.813 0.036 [193]
Moringa oleifera leaves powder NaOH þ Citric acid 303 3.080 10.32 42.92 [115]
Barley straw ash – 298 76.82 0.081 0.258 [120]
Litchi chinensis seeds – 24.45 27.05 0.010 [113]
Pb(II)
Chickpea husk KOH þ K2CO3 303 22.66 25.25 157.9 [190]
Sugarcane bagasse Pyrolysis þ H3PO4 303 11.54 39.99 0.020 [205]
Peanut husk Fe3O4 þ Iminodiacetic acid 298 0.650 19.40 0.070 [181]
Sugarcane bagasse Double mercerized þ succinic anhydride þ 1,3-diisopropyl – 29.59 – – [203]
carbodiimide
Sugarcane bagasse Double mercerized þ succinic anhydride þ acetic anhydride – 23.62 – – [203]
Marula seed husk – 293 4.620 60.46 0.220 [59]
Peanut shell – 293 – 16.68 25.16 [125]
Solanum melongena leaf – 323 8.746 3.698 0.039 [123]
Prunus dulcis seed shell powder Na2HPO4 283 1.720 14.22 56.19 [197]
Acorus calamus rhizome HCl 288 0.202 1.420 4.887 [162]
Acorus calamus rhizome NaOH 288 0.099 2.229 7.768 [162]
Jujube seeds Sulphuric acid 303 15.10 75.73 203.9 [169]
Cr(VI)
Citrus limettitoides peel Sulphuric acid 310 9.073 36.04 0.087 [164]
Date pit Epichlorohydrin þ diethylenetriamine 323 2.319 20.72 71.31 [206]
Olive stone Epichlorohydrin þ diethylenetriamine 293 2.913 21.67 64.21 [206]
Acorus calamus rhizome HCl 288 4.280 2.077 5.464 [162]
Acorus calamus rhizome NaOH 288 3.900 1.898 5.001 [162]
Zn(II)
Jujube seeds Sulphuric acid 303 13.41 66.21 175.7 [169]
Hg(II)
Cajanus cajan husk Ethanol þ NaOH þ CaCl2 303 5.590 81.13 203.9 [167]
As(III)
AC from Dialium guineense seed ZnCl2 348 344.4 51.68 192.6 [137]
shell

11
O. Ogunlalu et al.
ratio and conditions (like temperature) experimentally determined to
obtain maximum output. This is usually carried out after its pre-
treatment as shown in Fig. 3. It increases the amount of active binding
sites and enhances the ion-exchange properties of the adsorbent with the
heavy metal. Acidic activators are useful in the hydrolysis of cellulose,
lignin and hemicellulose present in the agricultural waste precursor.
Basic and neutral activators have been reported to aid in the removal of
lignin (deligninfication) and in some amounts of hemicellulose [207].
Common chemical activators used in the activation of agricultural wastes
for heavy metal remediation include mineral acids (such as HCl [116],
HNO3, H2SO4 [208,209], and H3PO4 [210,211]); alkalis (which include
NaOH [208,209], K2CO3 [212], and KOH [190,213]), and salts (ZnCl2
[214], CaCl2, FeCl2 and FeCl3 [215]).
Chemical activators are known to also introduce new functional
groups on the surface of the precursor as well as increase its porosity for
better adsorption [216]. The choice of chemical activating agent for the
production of very efficient adsorbents from agricultural waste is a
delicate issue and should involve factors such as the environmental
concerns that might arise with the process or disposing the process
wastes, higher adsorbent yield, overcoming energy losses, and its effect
on adsorption efficiency. While there is no doubt of the increase in effi-
ciency that chemical activation of agricultural wastes offers [217],
growing concerns have emerged over the past decades on the environ-
mental effects of using traditional chemical activators to activate the
agricultural waste.
Low cost Acorus calamus rhizome was treated with hydrochloric acid
and sodium hydroxide (Fig. 4) for the removal of Cr(VI) and Pb(II) ions
[162]. The characterization revealed an increase in the surface area of
the modified materials than in the pristine one. The maximum uptake for
Cr(VI) ions was 15.31, 23.86, 25.50 mg/g and Pb(II) ions 72.43, 76.09,
85.50 mg/g onto the pristine, acid-treated and base-treated materials
respectively. Though all 3 adsorbents proved to be effective, the modified
Fig. 3. Schematic diagram for processing of Agricultural wastes for adsorption [60].
12
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
materials slightly showed a better fit. The adsorption capacity of jujube
seed leaped from 16.72 mg/g to 221.1 mg/g after being treated with
sulphuric acid for the removal of Zn(II) ions [169], demonstrating the
heightened impact the modification has on the biomass.
In a recent research, Ghorbani, et al. [211] impregnated sugar beet
bagasse with phosphoric acid for the adsorption of Cr(VI) from solution.
It was observed that the activation process introduced the carbonyl,
carbon-carbon double bond, phosphorus and silicon peaks at 1693 cm1,
1593 cm1, 1068 cm1 and 793 cm1 respectively which were missing in
the unmodified adsorbent. The introduction of these functional groups
serves as additional active site for the attachment of the heavy metal. The
first phase of the modification process required 100  C at 24 h for drying
and another 100  C for 2 h to reflux. Afterwards, an additional temper-
ature of 85  C for 24 h was required to transform the sugar beet bagasse
to pellets. In the final step involving pyrolysis, a temperature of 450  C
was utilized in the steel reactor before a final drying process at 105  C for
12 h. Although this modified adsorbent afforded a removal efficiency of
50.45%, the high energy requirement in each step of the modification
process, especially for longer duration ranging from 12 to 24 h makes this
process relatively costly thereby limiting prospects for scaling.
€
Ozsin et al. [190] used two potassium-based bases; potassium hy-
droxide (KOH) and potassium carbonate (K2CO3) as chemical modifiers
for the modification of waste chickpea (Cicer arietinum) husk and com-
parison in adsorbent modification was drawn. A reduction in activated
carbon yield was observed for KOH in comparison with K2CO3 at all
impregnation ratios. This could be as a result of KOH ability to serve as a
better dehydrating agent and cause the elimination of volatile substances
from the surface of the adsorbent. The maximum specific surface area
recorded for the modified adsorbents were 2082 m2/g and 1921 m2/g
respectively for KOH and K2CO3 which signify a better adsorption ca-
pacity of KOH over K2CO3. Despite the high surface area of the
KOH-modified chickpea husk relative to the K2CO3-modified chickpea
O. Ogunlalu et al.
Fig. 4. Preparation of calamus rhizome (PCR), acid-treated calamus rhizome (ACR), and base-treated calamus rhizome (BCR) for adsorption [162].
husk and modest adsorption capacities of 135.8, 59.6, and 56.2 mg/g for
Pb(II), Cr(VI), and Cu(II) reported, the temperature required for this
modification is of economic concern. In the first step of modification, an
oven temperature of 85  C was required for 72 h. Afterwards, the
impregnated chickpea was placed in a steel reactor at 850  C for acti-
vation. Ultimately, further drying was carried out at 105  C after washing
to remove excess chemicals. The temperature required at each stage
particularly the longer duration (72 h) serves as a disadvantage of this
process. In addition, despite the moderate adsorption capacity of the
modified adsorbent, the use of potassium hydroxide as the modifying
agent also poses threat to the environment as being toxic even in low
concentrations to aquatic life. Modifying potassium carbonate which is
relatively cheap and non-toxic (classified as low hazard to the environ-
ment) with surface-improving additives and using it as a replacement for
potassium hydroxide could make this route greener, however, energy
requirement still has to be checked.
In a study by Pandey et al. [186], 0.5 M NaOH solution was employed
as a modifying agent for kush grass and bamboo leaves to adsorb Cd(II)
from aqueous solution. In their research, biomasses were sun-dried for
two days, ground and thoroughly washed them with double distilled
water. Subsequently, the biomasses were screened and modified with
0.5 M sodium hydroxide solution for 20 min before further drying at
100  C for a day to ensure complete dryness. The desorption study which
was carried out using nitric acid as an eluting agent revealed a desorption
efficiency of 94.18% and 92.08% for kush grass and bamboo leaves
respectively and a reuse cycle up to five. Although this suggests the
reusability of the adsorbents (kush grass and bamboo leaves), the rela-
tively high temperature (100  C) and the longer drying time associated
with the modification process serve as a disadvantages. In addition,
caution has been advised against the release of 0.5 M NaOH (and in
higher concentration) to the environment owing to its water ecology
toxicity which threatens aquatic life [218], therefore, the need to explore
other greener modifying agents.
Wang, Wang [184] utilized NaOH, succinic anhydride, and NaHCO3
for the surface modification of camphor leaf. Initially, leaf powder was
treated with 1.0 M NaOH solution at 25  C for 4 h with constant stirring.
Afterwards, the alkalized leaf powder was further treated with succinic
anhydride for 24 h under pyridine reflux after which it was treated with
13
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
sodium bicarbonate (NaHCO3) solution. Although some researchers have
suggested the relative greenness of some organic acids compared to
mineral acids, basic chemical activators such as NaOH are toxic partic-
ularly at high concentration. In another approach, Murugesan, et al.
[183] reported the modification of punnai shells using sulphuric acid.
However, a major concern with this process is the relatively high energy
of 400  C required to convert the shells to activated carbon (ash) in the
muffle furnace. Further to this, an additional temperature of 100  C was
required to dry the modified activated carbon after treating with sul-
phuric acid. The sulphuric acid used as a modifying reagent might have
significantly led to a heightened adsorption, its toxicity remains an
environmental concern and therefore the need for a greener modifying
agent.
Villabona-Ortiz et al. [219] impregnated corn residual biomass with
citric acid. This introduced a new peak at a wave number of 3340 cm1
which confirms the introduction of –OH functional group. In this study,
the oven-dried corn cobs were mixed with 0.5 M of citric acid and
continuously stirred at 60  C for 2 h. To ensure the total elimination of
the remaining citric acid, the modified corn cob was rinsed using
deionized water and subsequently dried at 55  C for 24 h. Although this
modification process required a longer drying time of 24 h, the drying
temperature is relatively moderate. Also, while the citric acid used as a
modifying agent in this research offers reduced environmental toxicity
(in comparison to mineral acids), organic acids may produce adsorbents
with significantly reduced adsorbent capacity and adsorbent yield.
Traditional acidic activators (HCl, HNO3, H2SO4, and H3PO4), basic
activators (KOH, NaOH) and neutral activators (CaCl2, ZnCl2) stand out
for higher surface area, give higher adsorbent yield, and enhance the
adsorption capacity of the agricultural waste in relation with other
greener activators [215]. Even though these traditional chemical acti-
vators give good result in lab and industrial scale settings, they are less
environmentally. They are corrosive, hazardous, and toxic at high con-
centrations and could lead to an explosion if heating is done after
impregnation and therefore should be handled with utmost care. Due to
the presence of ionic bonding in calcium chloride (CaCl2), it could
dissociate when discarded and can cause hardness when it comes into
contact with water bodies. Phosphoric acid (H3PO4), potassium hy-
droxide (KOH), and zinc chloride (ZnCl2) are the most commonly used
O. Ogunlalu et al.
acidic, basic and neutral activators respectively as they stand out in terms
of higher adsorbent yield, well-developed adsorbent pores, higher sur-
face area and higher adsorption capacity from other activators in their
respective groups [220]. In comparison with each other for industrial
scale-up, ZnCl2 should be discouraged as they produce lower adsorbent
yield and adsorbent capacity in comparison with the acidic or basic ac-
tivators, KOH should also be discouraged as they are more expensive and
are not commercially favourable even though they give high adsorbent
yield [220], better adsorbent properties and capacity. H3PO4, which is
more environmental-friendly than the other traditional acidic based ac-
tivators, could be encouraged at highly controlled conditions.
In trying to get alternatives that are more environmentally friendly,
various chemical activators have been tried by different researchers.
Organic acids such as acetic acid, citric acid, acrylic acid, glutamic acid
used in the production of cosmetics such as sanitizers, food and beverages
have been tried to serve as a replacement for the traditional acidic based
activators [208,219,221]. Results have shown that these chemicals
though friendlier produce adsorbents with poor adsorption capacity
which has discouraged its use on an industrial scale. Alternatives to
traditional basic based activators are carbonates and bicarbonate of po-
tassium and sodium such as potassium carbonate which has been found
to encourage the preservation of the precursor's morphology with lower
chances of causing explosion and acts as a dehydrating agent. Although
potassium carbonate produces higher adsorbent yield, in comparison
with traditional basic based activators such as KOH, it produces poorly
developed pores [194,215,220]. This has impeded the usage of these
type of activators in industrial scale. Other greener chemical activators
that have been explored in the activation of agricultural wastes for the
removal of heavy metals include potassium phosphate [222], potassium
hydrogen phosphate [223], sodium oxalate [223], succinic anhydride
[147], and EDTA [224]. Other greener chemical activators that could
also be explored in the remediation of heavy metals include sodium
thiosulphite, organic salts such as potassium citrate, potassium oxalate,
sodium gluconate, calcium citrate, zinc glyconate, potassium acetate, and
magnesium citrate. In an effort to increase the adsorption properties of
the various adsorbents with greener chemical activators, Yeneneh, et al.
[208] introduced additives such as urea, cetrimonium bromide (CTAB),
polyacrylamide (PAA), sodium methylate, and sodium dodecyl sulphate
(SDS) to bind with the adsorbent to further increase its adsorption ca-
pacity. Some improvement in adsorption was observed and therefore
future research could tread the line of using other additives on greener
chemical activators for adsorption processes and understanding the
mechanism of such process. Other additives that could be explored
include potassium chloride (KCl), Melamine, Ammonium dihydrogen
phosphate (NH4H2PO4), magnesium oxide (MgO), thiourea, and lithium
chloride (LiCl) [215].
Summarily, chemical modification has gained wider interest as a
method of surface modification which may be attributed to the enhanced
adsorption capacities if offers. However, the choice of modifying agents
depends on several factors including pore size, surface morphology,
thermal property, surface functional group and thermal properties
[225–227]. In the same vein, the chemical modification process of
agricultural wastes and process parameters including temperature de-
pends on the inherent waste properties. The implication of this is that an
outright recommendation of a modification process may be misleading as
the properties of the waste may influence the modification process and
the choice of modifying agent, therefore, caution must be taken.
8. Environmental issues associated with chemical modification
It is necessary to evaluate the effects a particular adsorbent might
pose to the environmental safety of the globe. After carrying out an
adsorption process, it is necessary to undertake a desorption experiment
which describes how many cycles an agricultural waste is able to
14
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
complete before being ripped off of its peak adsorption capacity. Com-
mon eluting solvents that are usually applied for this process cut across
strong acids and alkalis. In a research by Liu et al. [152], HNO3 was used
as an effective eluent and the sorbent could maintain close adsorption
capacities even after 10 reuse experiments. EDTA was employed in
another research by Li et al. [151] while a combination of HNO3 and
NaCl was required to remove adsorbed heavy metal ions from succiny-
lated okra biomass in another by Singha, Guleria [147]. During desorp-
tion, the protons present in an acid (which are most times relatively-more
concentrated than the metals they are trying to displace) compete with
the metal ions for the carboxylic groups in the agricultural waste and
consequently the adsorbed metal ions are displaced and washed away in
the loaded eluent. The ease at which the metal ions can be displaced by
the protons (or any other competing ion in case of non-acids) determines
the desorption efficiency. Comparison of studies that used HNO3 with
those that employed NaCl strictly showed that the former achieved more
desorption of the metal ions than the latter (when equal concentrations
are involved) because the Hþ ions showed higher displacement strength
than their Naþ counterparts. HCl also displayed excellent recovery in a
research by Tuzen, Sarı [228] and common cycles for effective reuse
ranged between 3 and 10 for all biomasses considered. Other eluents that
have been successfully employed for desorption studies include distilled
water, H2O2, NaOH, Na2CO3, NH4Cl and alum solution [16].
For waste disposal, different approaches are being churned out to
curb the imbalances these used sorbents tend to have on the environ-
ment. Some include biological treatments, advanced bio-physical pro-
cesses, ion exchange and most recently the application of catalytic
technologies [16]. Sorbents that have been used up and are incapable of
reuse can be burnt off at a very high temperature (preferably between
1100 and 1200 Celsius) and the resulting pollutant gases will be trapped
using specialized equipment [57].
9. Knowledge gap and future perspectives
Different chemical reagents ranging from acids, alkali, to salts have
been utilized as various adsorbent modifiers but more work needs to be
done to obtain better adsorbents that are environmentally friendly.
Several studies on the use of chemical modified agricultural wastes did
not take into consideration the effect of interfering ions that may be
present in environment laden with these heavy metals. It has been shown
that metal ions such as Na, Ca(II), Mg(II), and K may reduce the working
efficiency of the adsorbent [195]. In addition to this, more studies
involving the usage of these adsorbents in systems containing multiple
heavy metals in the same environment are needed to illustrate the effect
one heavy metal might induce in the uptake of another. In a similar
fashion, further research is encouraged on chemicals that would intro-
duce functional groups that would be able to adsorb various pollutants
just as they would be present in a real wastewater and the effect of one
pollutant on the uptake of another.
In line with the tenets of sustainable/green chemistry and since
chemical activation has been reported to increase the adsorption capacity
of the various adsorbents more than their corresponding unmodified
adsorbents, the use of more environmentally friendly chemicals should
be encouraged with a view to also encouraging the minimal usage of
these chemical reagents and the reduction in the amount of waste
generated [229].
The use of biological materials as precursors for nanoparticle syn-
thesis is gaining popularity as the secondary metabolites inherent in them
are used as reducing agents for metallic nanoparticles and also as
capping/stabilizing agents [230,231]. Most of the resulting nanoparticles
with reduced particle size, higher surface area, higher pore volume and
pore diameter are better adsorbents than their precursors [156]. There-
fore, more research should also be encouraged into the adsorbent opti-
mization of these chemical substances for the adsorption processes.
O. Ogunlalu et al.
10. Conclusion
This review focuses on the effect of chemical modification on several
agricultural wastes adsorbents for the uptake of various heavy metal ions,
it examines the progress made over the years in the adsorption of heavy
metal ions using unmodified and chemically-modified agricultural
wastes Details of adsorption of heavy metals by unmodified and
chemically-modified adsorbents are presented in this review including
adsorbent performance, adsorption kinetics and isotherms, adsorption
thermodynamics, and environmental issues associated with chemical
modification. These contents are comprehensively reviewed according to
recently published works of literature. Based on the adsorption energy
requirement, agricultural wastes such as eucalyptus wood/H2O2, Lansium
domesticum peel, and sugarcane bagasse showed some promises espe-
cially for industrial scale-up. Considering cost, environmental impact and
increase in adsorption properties caused by various chemical modifiers, it
was revealed that phosphoric acid is currently the best chemical modifier
even with its few demerits. We recommend that the reusability of these
chemically modified agricultural wastes should also be explored more to
determine the maximum number of cycles they can be used before they
lose their efficiency.
11. Ethics approval and consent to participate
Not applicable.
Funding
There was no external funding for the study.
12. Compliance with ethical standards
This article does not contain any studies involving human or animal
subjects.
13. Availability of data and materials
Not applicable.
Author contributions
Oluwafemi Ogunlalu, Conceptualisation, Writing - original draft; Data
curation; Writing - review & editing; Validation; Supervision.
Ifeoluwa Peter Oyekunle, Data curation; Writing - original draft;
Writing - review & editing; Validation.
Kingsley O. Iwuozor, Data curation; Writing - original draft; Writing -
review & editing; Validation.
Abiodun Daniel Aderibigbe, Conceptualisation, Writing - original draft;
Data curation; Writing - review & editing; Validation; Supervision.
Ebuka Chizitere Emenike, Data curation; Writing - original draft;
Writing - review & editing; Validation.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Declaration of competing interest
The authors declare that there are no conflicts of interest.
References
[1] P.S. Kumar, S. Ramalingam, S.D. Kirupha, A. Murugesan, T. Vidhyadevi,
S. Sivanesan, Adsorption behavior of nickel(II) onto cashew nut shell: equilibrium,
15
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
thermodynamics, kinetics, mechanism and process design, Chem. Eng. J. 167 (1)
(2011) 122–131, https://doi.org/10.1016/j.cej.2010.12.010.
[2] S. Mahdavi, Nano-TiO2 modified with natural and chemical compounds as
efficient adsorbents for the removal of Cdþ2, Cuþ2, and Niþ2 from water, Clean
Technol. Environ. Policy 18 (1) (2015) 81–94, https://doi.org/10.1007/s10098-
015-0993-y.
[3] J. Li, X. Wang, G. Zhao, C. Chen, Z. Chai, A. Alsaedi, et al., Metal-organic
framework-based materials: superior adsorbents for the capture of toxic and
radioactive metal ions, Chem. Soc. Rev. 47 (7) (2018) 2322–2356, https://
doi.org/10.1039/c7cs00543a.
[4] A.G. Adeniyi, J.O. Ighalo, Biosorption of pollutants by plant leaves: an empirical
review, J. Environ. Chem. Eng. 7 (3) (2019) 103100, https://doi.org/10.1016/
j.jece.2019.103100.
[5] Y. Cheng, P. He, F. Dong, X. Nie, C. Ding, S. Wang, et al., Polyamine and
amidoxime groups modified bifunctional polyacrylonitrile-based ion exchange
fibers for highly efficient extraction of U(VI) from real uranium mine water,
Chem. Eng. J. 367 (2019) 198–207, https://doi.org/10.1016/j.cej.2019.02.149.
[6] S. Yadav, H. Saleem, I. Ibrar, O. Naji, A.A. Hawari, A.A. Alanezi, et al., Recent
developments in forward osmosis membranes using carbon-based nanomaterials,
Desalination 482 (2020) 114375, https://doi.org/10.1016/j.desal.2020.114375.
[7] Ogemdi IK. Removal of Heavy Metals from Their Solution Using Polystyrene
Adsorbent (Foil Take-Away Disposable Plates).
[8] K.O. Iwuozor, E.E. Gold, Physico-chemical parameters of industrial effluents from
a brewery industry in Imo state, Nigeria, Adv. J. Chem. Sec. A 1 (2) (2018) 66–78.
[9] W. Nitayaphat, T. Jintakosol, Removal of silver(I) from aqueous solutions by
chitosan/bamboo charcoal composite beads, J. Clean. Prod. 87 (2015) 850–855,
https://doi.org/10.1016/j.jclepro.2014.10.003.
[10] R. Zhao, X. Li, B. Sun, M. Shen, X. Tan, Y. Ding, et al., Preparation of
phosphorylated polyacrylonitrile-based nanofiber mat and its application for
heavy metal ion removal, Chem. Eng. J. 268 (2015) 290–299, https://doi.org/
10.1016/j.cej.2015.01.061.
[11] M.L. Cantuaria, A.F. de Almeida Neto, E.S. Nascimento, M.G.A. Vieira, Adsorption
of silver from aqueous solution onto pre-treated bentonite clay: complete batch
system evaluation, J. Clean. Prod. 112 (2016) 1112–1121, https://doi.org/
10.1016/j.jclepro.2015.07.021.
[12] M. Huang, H. Tu, J. Chen, R. Liu, Z. Liang, L. Jiang, et al., Chitosan-rectorite
nanospheres embedded aminated polyacrylonitrile nanofibers via shoulder-to-
shoulder electrospinning and electrospraying for enhanced heavy metal removal,
Appl. Surf. Sci. 437 (2018) 294–303, https://doi.org/10.1016/
j.apsusc.2017.12.150.
[13] M. Chigondo, H.K. Paumo, M. Bhaumik, K. Pillay, A. Maity, Magnetic arginine-
functionalized polypyrrole with improved and selective chromium(VI) ions
removal from water, J. Mol. Liq. 275 (2019) 778–791, https://doi.org/10.1016/
j.molliq.2018.11.032.
[14] O.I. Peter, O.J. Adeyinka, R.A. Akolade, Application of snail shell chitosan as a
bioadsorbent in removal of copper (II) ions from wastewater, Earthline J. Chem.
Sci. (2019) 141–151, https://doi.org/10.34198/ejcs.2119.141151.
[15] C.A. Igwegbe, S.N. Oba, C.O. Aniagor, A.G. Adeniyi, J.O. Ighalo, Adsorption of
ciprofloxacin from water: a comprehensive review, J. Ind. Eng. Chem. 93 (2020)
57–77, https://doi.org/10.1016/j.jiec.2020.09.023.
[16] X. Xu, X. Hu, Z. Ding, Y. Chen, B. Gao, Waste-art-paper biochar as an effective
sorbent for recovery of aqueous Pb(II) into value-added PbO nanoparticles, Chem.
Eng. J. 308 (2017) 863–871, https://doi.org/10.1016/j.cej.2016.09.122.
[17] I.K. Ogemdi, Heavy metal concentration of aphrodisiac herbs locally sold in the
south-eastern region of Nigeria, Pharmaceutical Sci. Technol. 3 (1) (2019) 22.
[18] J.-F. Vigier, A. Laplace, C. Renard, M. Miguirditchian, F. Abraham, Uranium (III)-
Plutonium (III) co-precipitation in molten chloride, J. Nucl. Mater. 499 (2018)
394–400, https://doi.org/10.1016/j.jnucmat.2017.11.028.
[19] A. Zhul-quarnain, I.K. Ogemdi, I. Modupe, E. Gold, E.E. Chidubem, Adsorption of
malachite green dye using orange peel, J. Biomater. 2 (2) (2018) 31–40.
[20] Q. Fang, X. Zhou, W. Deng, Z. Liu, Hydroxyl-containing organic molecule induced
self-assembly of porous graphene monoliths with high structural stability and
recycle performance for heavy metal removal, Chem. Eng. J. 308 (2017)
1001–1009, https://doi.org/10.1016/j.cej.2016.09.139.
[21] Y. Wang, R. Qu, F. Pan, X. Jia, C. Sun, C. Ji, et al., Preparation and characterization
of thiol- and amino-functionalized polysilsesquioxane coated poly(p
-phenylenetherephthal amide) fibers and their adsorption properties towards
Hg(II), Chem. Eng. J. 317 (2017) 187–203, https://doi.org/10.1016/
j.cej.2017.02.073.
[22] G. Xu, Y. Zhao, L. Hou, J. Cao, M. Tao, W. Zhang, A recyclable phosphinic acid
functionalized polyacrylonitrile fiber for selective and efficient removal of Hg 2þ,
Chem. Eng. J. 325 (2017) 533–543, https://doi.org/10.1016/j.cej.2017.04.135.
[23] X. Xu, X. Cao, L. Zhao, H. Wang, H. Yu, B. Gao, Removal of Cu, Zn, and Cd from
aqueous solutions by the dairy manure-derived biochar, Environ. Sci. Pollut.
Control Ser. 20 (1) (2012) 358–368, https://doi.org/10.1007/s11356-012-0873-
5.
[24] L. Wang, Y. Wang, F. Ma, V. Tankpa, S. Bai, X. Guo, et al., Mechanisms and
reutilization of modified biochar used for removal of heavy metals from
wastewater: a review, Sci. Total Environ. 668 (2019) 1298–1309.
[25] K.G. Akpomie, J. Conradie, Banana peel as a biosorbent for the decontamination
of water pollutants, Rev. Environ. Chem. Let. 18 (4) (2020) 1085–1112.
[26] M. Hossain, H.H. Ngo, W. Guo, T. Nguyen, Removal of copper from water by
adsorption onto banana peel as bioadsorbent, Int. J. Geomate 2 (2) (2012)
227–234.
[27] G. Annadurai, R.-S. Juang, D. Lee, Adsorption of heavy metals from water using
banana and orange peels, Water Sci. Technol. 47 (1) (2003) 185–190.
O. Ogunlalu et al.
[28] K.G. Akpomie, J. Conradie, Advances in application of cotton-based adsorbents for
heavy metals trapping, surface modifications and future perspectives, Ecotoxicol.
Environ. Saf. 201 (2020) 110825.
[29] J. Ma, Y. Liu, O. Ali, Y. Wei, S. Zhang, Y. Zhang, et al., Fast adsorption of heavy
metal ions by waste cotton fabrics based double network hydrogel and influencing
factors insight, J. Hazard Mater. 344 (2018) 1034–1042.
[30] Y. Niu, W. Hu, M. Guo, Y. Wang, J. Jia, Z. Hu, Preparation of cotton-based fibrous
adsorbents for the removal of heavy metal ions, Carbohydr. Polym. 225 (2019)
115218.
[31] H.D. Ozsoy, H. Kumbur, Adsorption of Cu (II) ions on cotton boll, J. Hazard Mater.
136 (3) (2006) 911–916.
[32] A. Dadwal, V. Mishra, Review on biosorption of arsenic from contaminated water,
Clean 45 (7) (2017) 1600364.
[33] N.N. Rudi, M.S. Muhamad, L. Te Chuan, J. Alipal, S. Omar, N. Hamidon, et al.,
Evolution of adsorption process for manganese removal in water via agricultural
waste adsorbents, Heliyon 6 (9) (2020), e05049.
[34] H. Qin, T. Hu, Y. Zhai, N. Lu, J. Aliyeva, The improved methods of heavy metals
removal by biosorbents: a review, Environ. Pollut. 258 (2020) 113777.
[35] R.D. Ambashta, M. Sillanpaa, Water purification using magnetic assistance: a
review, J. Hazard Mater. 180 (1–3) (2010) 38–49, https://doi.org/10.1016/
j.jhazmat.2010.04.105.
[36] S.K.G. Methods, Of removing heavy metals from industrial wastewater,
J. Multidisci. Eng. Sci. Stud. 1 (1) (2015) 7.
[37] Z. Pan, L. An, Removal of heavy metal from wastewater using ion exchange
membranes, in: Applications of Ion Exchange Materials in the Environment,
Springer, 2019, pp. 25–46.
[38] K.O. Iwuozor, Prospects and challenges of using coagulation-flocculation method
in the treatment of effluents, Adv. J. Chem. Sec. A 2 (2) (2019) 105–127.
[39] J. Landaburu-Aguirre, E. Pongracz, P. Per€am€aki, R.L. Keiski, Micellar-enhanced
ultrafiltration for the removal of cadmium and zinc: use of response surface
methodology to improve understanding of process performance and optimisation,
J. Hazard Mater. 180 (1–3) (2010) 524–534.
[40] J. Huang, L. Peng, G. Zeng, X. Li, Y. Zhao, L. Liu, et al., Evaluation of micellar
enhanced ultrafiltration for removing methylene blue and cadmium ion
simultaneously with mixed surfactants, Separ. Purif. Technol. 125 (2014) 83–89.
[41] G.-M. Zeng, X. Li, J.-H. Huang, C. Zhang, C.-F. Zhou, J. Niu, et al., Micellar-
enhanced ultrafiltration of cadmium and methylene blue in synthetic wastewater
using SDS, J. Hazard Mater. 185 (2–3) (2011) 1304–1310.
[42] S. Petrov, V. Nenov, Removal and recovery of copper from wastewater by a
complexation-ultrafiltration process, Desalination 162 (2004) 201–209.
[43] C. Magnenet, F. Jurin, S. Lakard, C. Buron, B. Lakard, Polyelectrolyte modification
of ultrafiltration membrane for removal of copper ions, Colloid. Surface.
Physicochem. Eng. Aspect. 435 (2013) 170–177.
[44] R. Molinari, T. Poerio, P. Argurio, Selective separation of copper (II) and nickel (II)
from aqueous media using the complexation–ultrafiltration process, Chemosphere
70 (3) (2008) 341–348.
[45] J. Gao, Y. Qiu, B. Hou, Q. Zhang, X. Zhang, Treatment of wastewater containing
nickel by complexation-ultrafiltration using sodium polyacrylate and the stability
of PAA-Ni complex in the shear field, Chem. Eng. J. 334 (2018) 1878–1885.
[46] J. Shao, S. Qin, J. Davidson, W. Li, Y. He, H.S. Zhou, Recovery of nickel from
aqueous solutions by complexation-ultrafiltration process with sodium
polyacrylate and polyethylenimine, J. Hazard Mater. 244 (2013) 472–477.
[47] U. Danis, C. Aydiner, Investigation of process performance and fouling
mechanisms in micellar-enhanced ultrafiltration of nickel-contaminated waters,
J. Hazard Mater. 162 (2–3) (2009) 577–587.
[48] D.K. Jana, K. Roy, S. Dey, Comparative assessment on lead removal using micellar-
enhanced ultrafiltration (MEUF) based on a type-2 fuzzy logic and response
surface methodology, Separ. Purif. Technol. 207 (2018) 28–41.
[49] G. Son, S. Lee, Application of micellar enhanced ultrafiltration and activated
carbon fiber hybrid processes for lead removal from an aqueous solution, Kor. J.
Chem. Eng. 28 (3) (2011) 793–799.
[50] N. Abdullah, R. Gohari, N. Yusof, A. Ismail, J. Juhana, W. Lau, et al., Polysulfone/
hydrous ferric oxide ultrafiltration mixed matrix membrane: preparation,
characterization and its adsorptive removal of lead (II) from aqueous solution,
Chem. Eng. J. 289 (2016) 28–37.
[51] J. Landaburu-Aguirre, V. García, E. Pongracz, R.L. Keiski, The removal of zinc
from synthetic wastewaters by micellar-enhanced ultrafiltration: statistical design
of experiments, Desalination 240 (1–3) (2009) 262–269.
[52] J-h Huang, G-m Zeng, Y-h Qu, Z. Zhang, Adsorption characteristics of zinc ions on
sodium dodecyl sulfate in process of micellar-enhanced ultrafiltration, Trans.
Nonferrous Metals Soc. China 17 (5) (2007) 1112–1117.
[53] B. Rahmanian, M. Pakizeh, A. Maskooki, Micellar-enhanced ultrafiltration of zinc
in synthetic wastewater using spiral-wound membrane, J. Hazard Mater. 184
(1–3) (2010) 261–267.
[54] S. You, J. Lu, C.Y. Tang, X. Wang, Rejection of heavy metals in acidic wastewater
by a novel thin-film inorganic forward osmosis membrane, Chem. Eng. J. 320
(2017) 532–538, https://doi.org/10.1016/j.cej.2017.03.064.
[55] G. Crini, E. Lichtfouse, Advantages and disadvantages of techniques used for
wastewater treatment, Environ. Chem. Lett. 17 (1) (2019) 145–155.
[56] S.Y. Cheng, P.-L. Show, B.F. Lau, J.-S. Chang, T.C. Ling, New prospects for
modified algae in heavy metal adsorption, Trends Biotechnol. 37 (11) (2019)
1255–1268.
[57] Y. Zhou, X.-H. Xing, Z. Liu, L. Cui, A. Yu, Q. Feng, et al., Enhanced coagulation of
ferric chloride aided by tannic acid for phosphorus removal from wastewater,
Chemosphere 72 (2) (2008) 290–298.
16
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
[58] M. Cekim, S. Yildiz, T. Dere, Biosorption of copper from synthetic waters by using
tobacco leaf: equilibrum, Kinetic and Thermodynamic tests, J. Environ. Eng.
Landsc. Manag. 23 (3) (2015) 11, https://doi.org/10.3846/
16486897.2015.1050398, 10.3846/16486897.2012.721784.
[59] M. Moyo, U. Guyo, G. Mawenyiyo, N.P. Zinyama, B.C. Nyamunda, Marula seed
husk (Sclerocarya birrea) biomass as a low cost biosorbent for removal of Pb(II)
and Cu(II) from aqueous solution, J. Ind. Eng. Chem. 27 (2015) 126–132, https://
doi.org/10.1016/j.jiec.2014.12.026.
[60] H. Khatoon, J.P.N. Rai, Agricultural waste materials as biosorbents for the removal
of heavy metals and synthetic dyes-a review, Octa J. Environ. Res. 4 (3) (2016).
[61] L.A. Romero-Cano, H. García-Rosero, L.V. Gonzalez-Gutierrez, L.A. Baldenegro-
Perez, F. Carrasco-Marín, Functionalized adsorbents prepared from fruit peels:
equilibrium, kinetic and thermodynamic studies for copper adsorption in aqueous
solution, J. Clean. Prod. 162 (2017) 195–204, https://doi.org/10.1016/
j.jclepro.2017.06.032.
[62] D. Kołody nska, R. Wnętrzak, J. Leahy, M. Hayes, W. Kwapi nski, Z. Hubicki, Kinetic
and adsorptive characterization of biochar in metal ions removal, Chem. Eng. J.
197 (2012) 295–305.
[63] K.O. Iwuozor, Combustion of wood by pyrolysis: a review, Int. J. Atmos. Oceanic
Sci. 3 (1) (2019) 8, https://doi.org/10.11648/j.ijaos.20190301.11.
[64] K.O. Iwuozor, J.O. Ighalo, L.A. Ogunfowora, A.G. Adeniyi, C.A. Igwegbe, An
empirical literature analysis of adsorbent performance for methylene blue uptake
from aqueous media, J. Environ. Chem. Eng. (2021) 105658.
[65] X. Chen, G. Chen, L. Chen, Y. Chen, J. Lehmann, M.B. McBride, et al., Adsorption
of copper and zinc by biochars produced from pyrolysis of hardwood and corn
straw in aqueous solution, Bioresour. Technol. 102 (19) (2011) 8877–8884.
[66] N.D. Shooto, Removal of lead (II) and chromium (VI) ions from synthetic
wastewater by the roots of harpagophytum procumbens plant, J. Environ. Chem.
Eng. 8 (6) (2020) 104541.
[67] K.O. Iwuozor, T.A. Abdullahi, L.A. Ogunfowora, E.C. Emenike, O.P. Ifeoluwa,
F.A. Gbadamosi, J.O. Ighalo, Mitigation of Levofloxacin from Aqueous Media by
Adsorption: A Review, Sustainable Water Resources Management, 2021. Accepted
Manuscript, In press.
[68] N. Rajamohan, Biosorption of mercury onto protonated Pistachio hull wastes-
effect of variables and kinetic experiments, Int. J. Chem. Eng. Appl. 5 (5) (2014)
415.
[69] L. Semerjian, Removal of heavy metals (Cu, Pb) from aqueous solutions using pine
(Pinus halepensis) sawdust: equilibrium, kinetic, and thermodynamic studies,
Environ. Technol. Innovat. 12 (2018) 91–103.
[70] G.M. Al-Senani, F.F. Al-Fawzan, Adsorption study of heavy metal ions from
aqueous solution by nanoparticle of wild herbs, Egy. J. Aquat. Res. 44 (3) (2018)
187–194.
[71] T.K. Sen, A.F.B. Azman, S. Maitra, B.K. Dutta, Removal of mercury (II) from
aqueous solutions using the leaves of the rambai tree (Baccaurea motleyana),
Water Environ. Res. 83 (9) (2011) 834–842.
[72] K.G. Akpomie, L.O. Eluke, V.I.E. Ajiwe, C.O. Alisa, Attenuation kinetics and
desorption performance of artocarpus altilis seed husk for Co (II), Pb (II) and Zn
(II) Ions, Iran. J. Chem. Chem. Eng. (Int. Engl. Ed.) 37 (3) (2018) 171–186.
[73] F.A. Adekola, H.I. Adegoke, R.A. Ajikanle, Kinetic and equilibrium studies of Pb
(Ii) and Cd (Ii) adsorption on African wild mango (Irvingia gabonensis) Shell, Bull.
Chem. Soc. Ethiop. 30 (2) (2016) 185–198.
[74] D. Gümüş, Biosorptive application of defatted Laurus nobilis leaves as a waste
material for treatment of water contaminated with heavy metal, Int. J.
Phytoremediation 21 (6) (2019) 556–563.
[75] K.O. Iwuozor, J.O. Ighalo, E.C. Emenike, L.A. Ogunfowora, C.A. Igwegbe,
Adsorption of methyl orange: a review on adsorbent performance, Cur. Res. Green
Sust. Chem. 4 (2021) 16, https://doi.org/10.1016/j.crgsc.2021.100179.
[76] K. Naseem, R. Huma, A. Shahbaz, J. Jamal, M.Z.U. Rehman, A. Sharif, et al.,
Extraction of heavy metals from aqueous medium by husk biomass: adsorption
isotherm, kinetic and thermodynamic study, Z. Phys. Chem. 233 (2) (2019)
201–223.
[77] H.D. Ozsoy, Biosorptive removal of Hg (II) ions by Rhizopus oligosporus produced
from corn-processing wastewater, Afr. J. Biotechnol. 9 (51) (2010) 8783–8790.
[78] P.N. Diagboya, E.D. Dikio, Dynamics of mercury solid phase extraction using
Barbula lambarenensis, Environ. Technol. Innov. 9 (2018) 275–284.
[79] C. Egwuatu, I. Iloamaeke, C. Anarado, O. Umeohia, Locally sourced beans husk, a
potential adsorbent for Cd (II), Pb (II), Hg (II) ions in aqueous solution, Indian J.
Sci. Res. 4 (2013) 1129–1137.
[80] E. Chinyelu, U. Ngozi, O. Kate, O. Sixtus, Use of unmodified orange peel for the
adsorption of Cd (II), Pb (II) and Hg (II) ions in aqueous solutions, Am. J. Phys.
Chem. 4 (3) (2015) 21–29.
[81] N. Van Hien, E. Valsami-Jones, N.C. Vinh, T.T. Phu, N.T.T. Tam, I. Lynch,
Effectiveness of different biochar in aqueous zinc removal: correlation with
physicochemical characteristics, Biores. Technol. Reports 11 (2020) 100466.
[82] K. Rambabu, G. Bharath, F. Banat, P.L. Show, Biosorption performance of date
palm empty fruit bunch wastes for toxic hexavalent chromium removal, Environ.
Res. 187 (2020) 109694.
[83] R. Malik, S. Dahiya, An experimental and quantum chemical study of removal of
utmostly quantified heavy metals in wastewater using coconut husk: a novel
approach to mechanism, Int. J. Biol. Macromol. 98 (2017) 139–149.
[84] A. Sharma, K.G. Bhattacharyya, Azadirachta indica (Neem) leaf powder as a
biosorbent for removal of Cd(II) from aqueous medium, J. Hazard Mater. 125
(1–3) (2005) 102–112, https://doi.org/10.1016/j.jhazmat.2005.05.012.
[85] Z-l Chen, J-q Zhang, L. Huang, Z-h Yuan, Z-j Li, M-c Liu, Removal of Cd and Pb
with biochar made from dairy manure at low temperature, J. Integrat. Agricul. 18
(1) (2019) 201–210, https://doi.org/10.1016/s2095-3119(18)61987-2.
O. Ogunlalu et al.
[86] E. Cheraghi, E. Ameri, A. Moheb, Adsorption of cadmium ions from aqueous
solutions using sesame as a low-cost biosorbent: kinetics and equilibrium studies,
Int. J. Environ. Sci. Technol. 12 (8) (2015) 2579–2592, https://doi.org/10.1007/
s13762-015-0812-3.
[87] M.R. Sangi, A. Shahmoradi, J. Zolgharnein, G.H. Azimi, M. Ghorbandoost,
Removal and recovery of heavy metals from aqueous solution using Ulmus
carpinifolia and Fraxinus excelsior tree leaves, J. Hazard Mater. 155 (3) (2008)
513–522, https://doi.org/10.1016/j.jhazmat.2007.11.110.
[88] J. Igwe, N. Okoronkwo, C. Aghalibe, K. Onwuka, K. Achilike, E. Joseph, et al.,
Thermodynamics of Heavy Metals (Hg 2, Cd 2, Fe 2 and Ni 2) Adsorption Using
Boiler Fly Ash, 2020.
[89] L. Foo, C. Tee, N. Raimy, D. Hassell, L. Lee, Potential Malaysia agricultural waste
materials for the biosorption of cadmium (II) from aqueous solution, Clean
Technol. Environ. Policy 14 (2) (2012) 273–280.
[90] M.R.F. Oliveira, K. do Vale Abreu, A.L.E. Rom~ao, D.M.B. Davi, C.E. de Carvalho
Magalh~ aes, E.N.V.M. Carrilho, et al., Carnauba (Copernicia prunifera) palm tree
biomass as adsorbent for Pb (II) and Cd (II) from water medium, Environ. Sci.
Pollut. Control Ser. (2020) 1–12.
[91] Q. Cheng, Q. Huang, S. Khan, Y. Liu, Z. Liao, G. Li, et al., Adsorption of Cd by
peanut husks and peanut husk biochar from aqueous solutions, Ecol. Eng. 87
(2016) 240–245, https://doi.org/10.1016/j.ecoleng.2015.11.045.
[92] K.S. Rao, S. Anand, P. Venkateswarlu, Adsorption of cadmium from aqueous
solution by Ficus religiosa leaf powder and characterization of loaded biosorbent,
Clean 39 (4) (2011) 384–391, https://doi.org/10.1002/clen.201000098.
[93] Y.M. Isa, C. Harripersadth, P. Musonge, A. Sayago, M.G. Morales, The application
of eggshells and sugarcane bagasse as potential biomaterials in the removal of
heavy metals from aqueous solutions, S. Afr. J. Chem. Eng. 34 (1) (2020)
142–150.
[94] S.-Y. Lee, H.-J. Choi, Persimmon leaf bio-waste for adsorptive removal of heavy
metals from aqueous solution, J. Environ. Manag. 209 (2018) 382–392.
[95] D. Mohan, C.U. Pittman Jr., M. Bricka, F. Smith, B. Yancey, J. Mohammad, et al.,
Sorption of arsenic, cadmium, and lead by chars produced from fast pyrolysis of
wood and bark during bio-oil production, J. Colloid Interface Sci. 310 (1) (2007)
57–73, https://doi.org/10.1016/j.jcis.2007.01.020.
[96] F.H. Kamar, A.C. Nechifor, G. Nechifor, T.J. Al-Musawi, A.H. Mohammed,
Aqueous phase biosorption of Pb(II), Cu(II), and Cd(II) onto cabbage leaves
powder, Int. J. Chem. React. Eng. 15 (2) (2017), https://doi.org/10.1515/ijcre-
2015-0178.
[97] V.K. Gupta, C.K. Jain, I. Ali, M. Sharma, V.K. Saini, Removal of cadmium and
nickel from wastewater using bagasse fly ash—a sugar industry waste, Water Res.
37 (16) (2003) 4038–4044, https://doi.org/10.1016/s0043-1354(03)00292-6.
[98] G.H. Pino, L.M. Souza de Mesquita, M.L. Torem, G.A. Saavedra Pinto, Biosorption
of cadmium by green coconut shell powder, Miner. Eng. 19 (5) (2006) 380–387,
https://doi.org/10.1016/j.mineng.2005.12.003.
[99] S. Guiza, Biosorption of heavy metal from aqueous solution using cellulosic waste
orange peel, Ecol. Eng. 99 (2017) 134–140.
[100] M.S. Bagwan, P.R. Patil, Evaluation of removal efficiency of cu (II) ion by activated
carbon prepared from Nirgudi, Mudra and Gliricidia Sipium leaves from their
aqueous solution, Int. J. Adv. Chem. 2 (1) (2013), https://doi.org/10.14419/
ijac.v2i1.1863.
[101] M. Li, Q. Liu, L. Guo, Y. Zhang, Z. Lou, Y. Wang, et al., Cu(II) removal from
aqueous solution by Spartina alterniflora derived biochar, Bioresour. Technol. 141
(2013) 83–88, https://doi.org/10.1016/j.biortech.2012.12.096.
[102] U.M.K. Nagpal, A.V. Bankar, N.J. Pawar, B.P. Kapadnis, S.S. Zinjarde, Equilibrium
and kinetic studies on biosorption of heavy metals by leaf powder of paper
mulberry (broussonetia papyrifera), Water Air Soil Pol. 215 (1–4) (2010)
177–188, https://doi.org/10.1007/s11270-010-0468-z.
[103] Z. Mahdi, Q.J. Yu, A. El Hanandeh, Investigation of the kinetics and mechanisms
of nickel and copper ions adsorption from aqueous solutions by date seed derived
biochar, J. Environ. Chem. Eng. 6 (1) (2018) 1171–1181.
[104] H. Aydin, Y. Bulut, C. Yerlikaya, Removal of copper (II) from aqueous solution by
adsorption onto low-cost adsorbents, J. Environ. Manag. 87 (1) (2008) 37–45,
https://doi.org/10.1016/j.jenvman.2007.01.005.
[105] R.M. Ali, H.A. Hamad, M.M. Hussein, G.F. Malash, Potential of using green
adsorbent of heavy metal removal from aqueous solutions: adsorption kinetics,
isotherm, thermodynamic, mechanism and economic analysis, Ecol. Eng. 91
(2016) 317–332.
[106] X. Chen, G. Chen, L. Chen, Y. Chen, J. Lehmann, M.B. McBride, et al., Adsorption
of copper and zinc by biochars produced from pyrolysis of hardwood and corn
straw in aqueous solution, Bioresour. Technol. 102 (19) (2011) 8877–8884,
https://doi.org/10.1016/j.biortech.2011.06.078.
[107] I. Abdelfattah, A.A. Ismail, F.A. Sayed, A. Almedolab, K.M. Aboelghait, Biosorption
of heavy metals ions in real industrial wastewater using peanut husk as efficient
and cost effective adsorbent, Environ. Nanotechnol. Monit. Manag. 6 (2016)
176–183, https://doi.org/10.1016/j.enmm.2016.10.007.
[108] W.S. Wan Ngah, M.A.K.M. Hanafiah, Adsorption of copper on rubber (Hevea
brasiliensis) leaf powder: kinetic, equilibrium and thermodynamic studies,
Biochem. Eng. J. 39 (3) (2008) 521–530, https://doi.org/10.1016/
j.bej.2007.11.006.
[109] Olim D, Afu S, Adie P, Akpa E. Adsorption Kinetics of Copper, Lead and Zinc by
Cow Dung, Poultry Manure and Cocoa (Theobroma Cacao) Pod.
[110] E.S.Z. El-Ashtoukhy, N.K. Amin, O. Abdelwahab, Removal of lead (II) and copper
(II) from aqueous solution using pomegranate peel as a new adsorbent,
Desalination 223 (1–3) (2008) 162–173, https://doi.org/10.1016/
j.desal.2007.01.206.
17
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
[111] S. Ben-Ali, I. Jaouali, S. Souissi-Najar, A. Ouederni, Characterization and
adsorption capacity of raw pomegranate peel biosorbent for copper removal,
J. Clean. Prod. 142 (2017) 3809–3821.
[112] S. Uçar, M. Erdem, T. Tay, S. Karag€ oz, Removal of lead (II) and nickel (II) ions
from aqueous solution using activated carbon prepared from rapeseed oil cake by
Na 2 CO 3 activation, Clean Technol. Environ. Policy 17 (3) (2015) 747–756.
[113] J.G. Flores-Garnica, L. Morales-Barrera, G. Pineda-Camacho, E. Cristiani-Urbina,
Biosorption of Ni(II) from aqueous solutions by Litchi chinensis seeds, Bioresour.
Technol. 136 (2013) 635–643, https://doi.org/10.1016/j.biortech.2013.02.059.
[114] R. Sudha, K. Srinivasan, P. Premkumar, Removal of nickel(II) from aqueous
solution using Citrus Limettioides peel and seed carbon, Ecotoxicol. Environ.
safety 117 (2015) 115–123, https://doi.org/10.1016/j.ecoenv.2015.03.025.
[115] D.H.K. Reddy, K. Seshaiah, A.V.R. Reddy, S.M. Lee, Optimization of Cd(II), Cu(II)
and Ni(II) biosorption by chemically modified Moringa oleifera leaves powder,
Carbohydr. Polym. 88 (3) (2012) 1077–1086, https://doi.org/10.1016/
j.carbpol.2012.01.073.
 Villabona-Ortiz, C. Tejada-Tovar, A.D.
[116] A.  Gonzalez-Delgado, A. Herrera-Barros,
R. Silvera-Charris, Removal of Cr(VI) ions from aqueous solution using orange peel
residual biomass: thermodynamic and sorption-desorption study, Desalin.Water
Treat. 203 (2020) 309–314, https://doi.org/10.5004/dwt.2020.26237.
[117] K.A. Shroff, V.K. Vaidya, Kinetics and equilibrium studies on biosorption of nickel
from aqueous solution by dead fungal biomass of Mucor hiemalis, Chem. Eng. J.
171 (3) (2011) 1234–1245, https://doi.org/10.1016/j.cej.2011.05.034.
[118] E. Malkoc, Y. Nuhoglu, Investigations of nickel(II) removal from aqueous solutions
using tea factory waste, J. Hazard Mater. 127 (1–3) (2005) 120–128, https://
doi.org/10.1016/j.jhazmat.2005.06.030.
[119] Y.F. Lam, L.Y. Lee, S.J. Chua, S.S. Lim, S. Gan, Insights into the equilibrium, kinetic
and thermodynamics of nickel removal by environmental friendly Lansium
domesticum peel biosorbent, Ecotoxicol. Environ. safety 127 (2016) 61–70,
https://doi.org/10.1016/j.ecoenv.2016.01.003.
[120] M. Arshadi, M.J. Amiri, S. Mousavi, Kinetic, equilibrium and thermodynamic
investigations of Ni(II), Cd(II), Cu(II) and Co(II) adsorption on barley straw ash,
Water Res. Indus. 6 (2014) 1–17, https://doi.org/10.1016/j.wri.2014.06.001.
[121] I. Aloma, M.A. Martín-Lara, I.L. Rodríguez, G. Blazquez, M. Calero, Removal of
nickel (II) ions from aqueous solutions by biosorption on sugarcane bagasse,
J. Taiwan Ins. Chem. Eng. 43 (2012) 7, https://doi.org/10.1016/
j.jtice.2011.10.011.
[122] R. Baby Shaikh, B. Saifullah, F.U. Rehman, Greener method for the removal of
toxic metal ions from the wastewater by application of agricultural waste as an
adsorbent, Water 10 (10) (2018) 1316.
[123] G. Yuvaraja, N. Krishnaiah, M.V. Subbaiah, A. Krishnaiah, Biosorption of Pb(II)
from aqueous solution by Solanum melongena leaf powder as a low-cost
biosorbent prepared from agricultural waste, Colloids Surf. B Biointerfaces 114
(2014) 75–81, https://doi.org/10.1016/j.colsurfb.2013.09.039.
[124] A.D. A, O.U. O, O.O. O, I.A. A, Adsorption studies of Pb2þ from aqueous solutions
using unmodified and citric acid – modified plantain (musa paradisiaca) peels,
IOSR J. Appl. Chem. 10 (2) (2017) 30–39, https://doi.org/10.9790/5736-
1002013039.
€
[125] Ş. Taşar, F. Kaya, A. Ozer, Biosorption of lead(II) ions from aqueous solution by
peanut shells: equilibrium, thermodynamic and kinetic studies, J. Environ. Chem.
Eng. 2 (2) (2014) 1018–1026, https://doi.org/10.1016/j.jece.2014.03.015.
[126] M. Sekar, V. Sakthi, S. Rengaraj, Kinetics and equilibrium adsorption study of
lead(II) onto activated carbon prepared from coconut shell, J. Colloid Interface Sci.
279 (2) (2004) 307–313, https://doi.org/10.1016/j.jcis.2004.06.042.
[127] Aguilar DLG, Miranda JPR, Mu~ noz JAE. BIOADSORPTION OF LEAD (II) WITH
COFFEE PULP IN SYNTHETIC WASTEWATER.
[128] E.D. Asuquo, A.D. Martin, Sorption of cadmium (II) ion from aqueous solution
onto sweet potato (Ipomoea batatas L.) peel adsorbent: characterisation, kinetic
and isotherm studies, J. Environ. Chem. Eng. 4 (4) (2016) 4207–4228, https://
doi.org/10.1016/j.jece.2016.09.024.
[129] F.A. Dawodu, B.M. Akpan, K.G. Akpomie, Sequestered capture and desorption of
hexavalent chromium from solution and textile wastewater onto low cost Heinsia
crinita seed coat biomass, Appl. Water Sci. 10 (1) (2020) 1–15.
[130] S.-H. Peng, R. Wang, L.-Z. Yang, L. He, X. He, X. Liu, Biosorption of copper, zinc,
cadmium and chromium ions from aqueous solution by natural foxtail millet shell,
Ecotoxicol. Environ. Saf. 165 (2018) 61–69.
[131] E. Kalipci, O.O. Namal, Removal of Cr (VI) using a novel adsorbent modification.
Ultrasonic method with apricot kernel shells, Environ. Protect. Eng. 44 (3) (2018).
[132] R.-M. Naik, S. Ratan, I. Singh, Use of Orange Peel as an Adsorbent for the Removal
of Cr (VI) from its Aqueous Solution, 2018.
[133] P. Tiwari, M.C. Vishwakarma, S.K. Joshi, H. Sharma, N.S. Bhandari, Adsorption of
Pb (II), Cu (II), and Zn (II) Ions onto Urtica dioica leaves (UDL) as a low cost
adsorbent: equilibrium and thermodynamic studies, Mod. Chem. 5 (2017) 11–18.
[134] A. Elham, T. Hossein, H. Mahnoosh, Removal of Zn (II) and Pb (II) ions using rice
husk in food industrial wastewater, J. Appl. Sci. Environ. Manag. 14 (4) (2010).
[135] S. Shukla, R.S. Pai, Adsorption of Cu (II), Ni (II) and Zn (II) on dye loaded
groundnut shells and sawdust, Separ. Purif. Technol. 43 (1) (2005) 1–8.
[136] S. Shukla, R.S. Pai, Adsorption of Cu (II), Ni (II) and Zn (II) on modified jute fibres,
Bioresour. Technol. 96 (13) (2005) 1430–1438.
[137] J.U. Ani, A.E. Ochonogor, K.G. Akpomie, C.S. Olikagu, C.C. Igboanugo,
Abstraction of arsenic (III) on activated carbon prepared from Dialium guineense
seed shell: kinetics, isotherms and thermodynamic studies, SN Appl. Sci. 1 (10)
(2019) 1–11.
[138] J.A. Baig, T.G. Kazi, A.Q. Shah, G.A. Kandhro, H.I. Afridi, S. Khan, et al.,
Biosorption studies on powder of stem of Acacia nilotica: removal of arsenic from
surface water, J. Hazard Mater. 178 (1–3) (2010) 941–948.
O. Ogunlalu et al.
[139] P. Kumari, P. Sharma, S. Srivastava, M. Srivastava, Biosorption studies on shelled
Moringa oleifera Lamarck seed powder: removal and recovery of arsenic from
aqueous system, Int. J. Miner. Process. 78 (3) (2006) 131–139.
[140] D. Ranjan, M. Talat, S. Hasan, Biosorption of arsenic from aqueous solution using
agricultural residue ‘rice polish’, J. Hazard Mater. 166 (2–3) (2009) 1050–1059.
[141] M. Arshadi, M.J. Amiri, S. Mousavi, Kinetic, equilibrium and thermodynamic
investigations of Ni (II), Cd (II), Cu (II) and Co (II) adsorption on barley straw ash,
Water Res. Indus. 6 (2014) 1–17.
[142] F. Güzel, H. Yakut, G. Topal, Determination of kinetic and equilibrium parameters
of the batch adsorption of Mn (II), Co (II), Ni (II) and Cu (II) from aqueous solution
by black carrot (Daucus carota L.) residues, J. Hazard Mater. 153 (3) (2008)
1275–1287.
[143] A. Obike, J. Igwe, C. Emeruwa, K. Uwakwe, Equilibrium and kinetic studies of Cu
(II), Cd (II), Pb (II) and Fe (II) adsorption from aqueous solution using cocoa
(Theobroma cacao) pod husk, J. Appl. Sci. Environ. Manag. 22 (2) (2018)
182–190, 90.
[144] F. Adekola, D. Hodonou, H. Adegoke, Thermodynamic and kinetic studies of
biosorption of iron and manganese from aqueous medium using rice husk ash,
Appl. Water Sci. 6 (4) (2016) 319–330.
[145] M.P. Tavlieva, S.D. Genieva, V.G. Georgieva, L.T. Vlaev, Thermodynamics and
kinetics of the removal of manganese (II) ions from aqueous solutions by white
rice husk ash, J. Mol. Liq. 211 (2015) 938–947.
[146] C. Tejada-Tovar, A. Villabona-Ortíz, A. Herrera-Barros, A.  Gonzalez-Delgado,
L. Garces, Adsorption kinetics of Cr (VI) using modified residual biomass in batch
and continuous system, Indian J. Sci. Technol. 11 (14) (2018) 1–8.
[147] A.S. Singha, A. Guleria, Utility of chemically modified agricultural waste okra
biomass for removal of toxic heavy metal ions from aqueous solution, Eng. Agri.
Environ. Food 8 (1) (2015) 52–60, https://doi.org/10.1016/j.eaef.2014.08.001.
[148] M.E. Brassesco, N.W. Valetti, G. Pic o, Molecular mechanism of lysozyme
adsorption onto chemically modified alginate guar gum matrix, Int. J. Biol.
Macromol. 96 (2017) 111–117.
[149] H. Wang, X. Jin, H. Wu, Adsorption and desorption properties of modified feather
and feather/polypropylene melt-blown filter cartridge of lead ion (Pb2þ), J. Ind.
Textil. 46 (3) (2016) 852–867.
[150] T. Cai, X. Liu, J. Zhang, B. Tie, M. Lei, X. Wei, et al., Silicate-modified oiltea
camellia shell-derived biochar: a novel and cost-effective sorbent for cadmium
removal, J. Clean. Prod. 281 (2021) 125390.
[151] T-t Li, Y-g Liu, Q-q Peng, X-j Hu, T. Liao, H. Wang, et al., Removal of lead (II) from
aqueous solution with ethylenediamine-modified yeast biomass coated with
magnetic chitosan microparticles: kinetic and equilibrium modeling, Chem. Eng. J.
214 (2013) 189–197.
[152] B. Liu, W. Chen, X. Peng, Q. Cao, Q. Wang, D. Wang, et al., Biosorption of lead
from aqueous solutions by ion-imprinted tetraethylenepentamine modified
chitosan beads, Int. J. Biol. Macromol. 86 (2016) 562–569.
[153] Y. Niu, K. Li, D. Ying, Y. Wang, J. Jia, Novel recyclable adsorbent for the removal
of copper (II) and lead (II) from aqueous solution, Bioresour. Technol. 229 (2017)
63–68.
[154] Z. Kovacova, S. Demcak, M. Balintova, C. Pla, I. Zinicovscaia, Influence of wooden
sawdust treatments on Cu (II) and Zn (II) removal from water, Materials 13 (16)
(2020) 3575.
[155] M. Gupta, H. Gupta, D. Kharat, Adsorption of Cu (II) by low cost adsorbents and
the cost analysis, Environ. Technol. Innovat. 10 (2018) 91–101.
[156] H. Yu, J. Liu, J. Shen, X. Sun, J. Li, L. Wang, Preparation of MnOx-loaded biochar
for Pb2þ removal: adsorption performance and possible mechanism, J. Taiwan
Ins. Chem. Eng. 66 (2016) 313–320.
[157] H. Lin, J. Xu, Y. Dong, L. Wang, W. Xu, Y. Zhou, Adsorption of heavy metal
cadmium (II) ions using chemically modified corncob: mechanism, kinetics, and
thermodynamics, Desalin.Water Treat. 57 (39) (2016) 18537–18550.
[158] E. Pehlivan, T. Altun, S. Parlayici, Modified barley straw as a potential biosorbent
for removal of copper ions from aqueous solution, Food Chem. 135 (4) (2012)
2229–2234, https://doi.org/10.1016/j.foodchem.2012.07.017.
[159] W. Kong, J. Ren, S. Wang, Q. Chen, Removal of heavy metals from aqueous
solutions using acrylic-modified sugarcane bagasse-based adsorbents: equilibrium
and kinetic studies, BioResources 9 (2) (2014) 3184–3196.
[160] C.P. Okoli, P.N. Diagboya, I.O. Anigbogu, B.I. Olu-Owolabi, K.O. Adebowale,
Competitive biosorption of Pb (II) and Cd (II) ions from aqueous solutions using
chemically modified moss biomass (Barbula lambarenensis), Environ. Earth Sci.
76 (1) (2017) 1–10.
[161] S. Boeykens, N. Redondo, R.A. Obeso, N. Caracciolo, C. Vazquez, Chromium and
Lead adsorption by avocado seed biomass study through the use of Total
Reflection X-Ray Fluorescence analysis, Appl. Radiat. Isot. 153 (2019) 108809.
[162] N.D. Shooto, Removal of toxic hexavalent chromium (Cr (VI)) and divalent lead
(Pb (II)) ions from aqueous solution by modified rhizomes of Acorus calamus, Surf.
Interf. 20 (2020) 100624.
[163] P.M. Thabede, N.D. Shooto, T. Xaba, E.B. Naidoo, Adsorption studies of toxic
cadmium (II) and chromium (VI) ions from aqueous solution by activated black
cumin (Nigella sativa) seeds, J. Environ. Chem. Eng. 8 (4) (2020) 104045.
[164] P. Premkumar, S. Ramasamy, Comparative studies on the removal of chromium
(VI) from aqueous solutions using raw and modified Citrus Limettioides peel,
Indian J. Chem. Technol. 25 (3) (2018) 255–265.
[165] C. Tejada-Tovar, A. Herrera-Barros, A. Villabona-Ortíz, A.  Gonzalez-Delgado,
J. Nú~ nez-Zarur, Hexavalent chromium adsorption from aqueous solution using
orange peel modified with calcium chloride: equilibrium and kinetics study,
Indian J. Sci. Technol. 11 (17) (2018) 1–10.
18
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
[166] Z. Ding, R. Yu, X. Hu, Y. Chen, Adsorptive removal of Hg (II) ions from aqueous
solutions using chemical-modified peanut hull powder, Pol. J. Environ. Stud. 23
(4) (2014).
[167] M.A. Devani, B. Munshi, J.U.K. Oubagaranadin, B.B. Lal, S. Mandal, Remediation
of Hg (II) from solutions using Cajanus cajan husk as a new sorbent, Environ.
Technol. 38 (15) (2017) 1878–1886.
[168] N.D. Shooto, P.M. Thabede, E.B. Naidoo, Simultaneous adsorptive study of toxic
metal ions in quaternary system from aqueous solution using low cost black cumin
seeds (Nigella sativa) adsorbents, S. Afr. J. Chem. Eng. 30 (2019) 15–27.
[169] R. Gayathri, K. Gopinath, P.S. Kumar, Adsorptive separation of toxic metals from
aquatic environment using agro waste biochar: application in electroplating
industrial wastewater, Chemosphere 262 (2021) 128031.
[170] M. Abid, N.K. Niazi, I. Bibi, A. Farooqi, Y.S. Ok, A. Kunhikrishnan, et al., Arsenic
(V) biosorption by charred orange peel in aqueous environments, Int. J.
Phytoremediation 18 (5) (2016) 442–449.
[171] A. Ali, K. Saeed, Decontamination of Cr (VI) and Mn (II) from aqueous media by
untreated and chemically treated banana peel: a comparative study, Desalin.Water
Treat. 53 (13) (2015) 3586–3591.
[172] S. Manjunath, S.M. Kumar, H.H. Ngo, W. Guo, Metronidazole removal in powder-
activated carbon and concrete-containing graphene adsorption systems:
estimation of kinetic, equilibrium and thermodynamic parameters and
optimization of adsorption by a central composite design, J. Environ. Sci. Health A
52 (14) (2017) 1269–1283.
[173] B. Yao, D. Zhi, Y. Zhou, Iron-based materials for removal of arsenic from water, in:
Sorbents Materials for Controlling Environmental Pollution, Elsevier, 2021,
pp. 209–245.
[174] M.A. Al-Ghouti, D.A. Da'ana, Guidelines for the use and interpretation of
adsorption isotherm models: a review, J. Hazard Mater. 393 (2020) 122383,
https://doi.org/10.1016/j.jhazmat.2020.122383.
[175] S. Kulkarni, S. Dhokpande, A review on isotherms and kinetics of heavy metal
removal, Int. J. Ethics Eng. Manag. Ed. 1 (2) (2014) 1–4.
[176] Z. Al-Qodah, M.A. Yahya, M. Al-Shannag, On the performance of bioadsorption
processes for heavy metal ions removal by low-cost agricultural and natural by-
products bioadsorbent: a review, Desalin.Water Treat. 85 (2017) 339–357.
[177] I. Langmuir, The adsorption of gases on plane surfaces of glass, mica and platinum,
J. Am. Chem. Soc. 40 (9) (1918) 1361–1403.
[178] K.O. Iwuozor, I.P. Oyekunle, I.O. Oladunjoye, E.M. Ibitogbe, T.S. Olorunfemi,
A review on the mitigation of heavy metals from aqueous solution using sugarcane
bagasse, SugarTech (2021), https://doi.org/10.1007/s12355-021-01051-w.
Accepted Manuscript.
[179] Y.-S. Ho, G. McKay, Application of kinetic models to the sorption of copper (II) on
to peat, Adsorpt. Sci. Technol. 20 (8) (2002) 797–815.
[180] O.J. Akinyeye, T.B. Ibigbami, O.O. Odeja, O.M. Sosanolu, Evaluation of kinetics
and equilibrium studies of biosorption potentials of bamboo stem biomass for
removal of Lead (II) and Cadmium (II) ions from aqueous solution, Afr. J. Pure
Appl. Chem. 14 (2) (2020) 24–41.
[181] A.A. Aryee, F.M. Mpatani, Y. Du, A.N. Kani, E. Dovi, R. Han, et al., Fe3O4 and
iminodiacetic acid modified peanut husk as a novel adsorbent for the uptake of Cu
(II) and Pb (II) in aqueous solution: characterization, equilibrium and kinetic
study, Environ. Pollut. 268 (2021) 115729.
[182] A. Daochalermwong, N. Chanka, K. Songsrirote, P. Dittanet, C. Niamnuy,
A. Seubsai, Removal of heavy metal ions using modified celluloses prepared from
pineapple leaf fiber, ACS Omega 5 (10) (2020) 5285–5296.
[183] A. Murugesan, M. Divakaran, P. SenthilKumar, Enhanced adsorption of Cu2þ, Ni2
þ, Cd2þ and Zn2þ ions onto physico-chemically modified agricultural waste:
kinetic, isotherm and thermodynamic studies, Desalin.Water Treat. 122 (2018)
176–191.
[184] C. Wang, H. Wang, Carboxyl functionalized Cinnamomum camphora for removal
of heavy metals from synthetic wastewater-contribution to sustainability in
agroforestry, J. Clean. Prod. 184 (2018) 921–928.
[185] R. Baby, M.Z. Hussein, Ecofriendly approach for treatment of heavy-metal-
contaminated water using activated carbon of kernel shell of oil Palm, Materials
13 (11) (2020) 2627.
[186] R. Pandey, R.L. Prasad, N.G. Ansari, R.C. Murthy, Utilization of NaOH modified
Desmostachya bipinnata (Kush grass) leaves and Bambusa arundinacea (bamboo)
leaves for Cd(II) removal from aqueous solution, J. Environ. Chem. Eng. 3 (1)
(2015) 593–602, https://doi.org/10.1016/j.jece.2014.06.015.
[187] E. de Souza, A. Pimenta, A. da Silva, R. Braga, T. de Azevedo, P. de Medeiros Neto,
Efficiency of H2 O2-treated eucalyptus biochar on the removal of Cu (II), Cd (II)
and Ni (II) from aqueous solution, Rev. Bras. Ci^encia Avícola 15 (3) (2020).
[188] A. Kenessova, G. Seilkhanova, A. Rakhym, Y. Mastai, Composite materials based
on orange and pomegranate peels for Сu (II) and Zn (II) ions extraction, Int. J.
Biol. Chem. 13 (1) (2020) 154–160.
[189] Y. Chen, H. Shi, H. Guo, C. Ling, X. Yuan, P. Li, Hydrated titanium oxide
nanoparticles supported on natural rice straw for Cu (II) removal from water,
Environ. Technol. Innov. 20 (2020) 101143.
€
[190] G. Ozsin, M. Kılıç, E. Apaydın-Varol, A.E. Pütün, Chemically activated carbon
production from agricultural waste of chickpea and its application for heavy metal
adsorption: equilibrium, kinetic, and thermodynamic studies, Appl. Water Sci. 9
(3) (2019), https://doi.org/10.1007/s13201-019-0942-8.
[191] V. Halysh, O. Sevastyanova, S. Pikus, G. Dobele, B. Pasalskiy, V.M. Gun’ko, et al.,
Sugarcane bagasse and straw as low-cost lignocellulosic sorbents for the removal
of dyes and metal ions from water, Cellulose 27 (14) (2020) 8181–8197.
[192] M.A. Akl, Biosorption of copper(II) and lead(II) ions from aqueous solutions by
modified loquat (Eriobotrya japonica) leaves (MLL), J. Chem. Eng. Mater. Sci. 3
(1) (2012), https://doi.org/10.5897/jcems11.061.
O. Ogunlalu et al.
[193] Y. Wu, Y. Fan, M. Zhang, Z. Ming, S. Yang, A. Arkin, et al., Functionalized
agricultural biomass as a low-cost adsorbent: utilization of rice straw incorporated
with amine groups for the adsorption of Cr (VI) and Ni (II) from single and binary
systems, Biochem. Eng. J. 105 (2016) 27–35.
[194] D. A, A. R, Modified Mangosteen shell carbon in the removal of Pb (II) and Hg (II)
from aqueous solution-Isotherm and Kinetic studies, Global NEST J. 23 (1) (2021)
7, https://doi.org/10.30955/gnj.003188.
[195] Y. Liu, Q. Gao, S. Pu, H. Wang, K. Xia, B. Han, et al., Carboxyl-functionalized lotus
seedpod: a highly efficient and reusable agricultural waste-based adsorbent for
removal of toxic Pb2þ ions from aqueous solution, Colloid. Surface. Physicochem.
Eng. Aspect. 568 (2019) 391–401.
[196] K. Prabhakar, Preparation and characterization of activated carbon from Acacia
arabica and its potentiality in the removal of lead by adsorption, J. Adv. Stud.
Agri. Biol. Environ. Sci. 3 (4) (2016) 11.
[197] C.U. Ibeji, K.G. Akpomie, C.I. Ugwu, B.A. Agwogie, S.A. Ogundare, J.F. Amaku,
Sequestration of Pb (II) onto phosphate modified fibrous prunus dulcis seed shell:
kinetic, thermodynamic, isotherm, desorption and reusability, J. Nat. Fibers
(2020) 1–14.
[198] V. Lugo-Lugo, C. Barrera-Díaz, F. Ure~ na-Nú~nez, B. Bilyeu, I. Linares-Hernandez,
Biosorption of Cr (III) and Fe (III) in single and binary systems onto pretreated
orange peel, J. Environ. Manag. 112 (2012) 120–127.
[199] A. García-Mendieta, M.T. Olguín, M. Solache-Ríos, Biosorption properties of green
tomato husk (Physalis philadelphica Lam) for iron, manganese and
iron–manganese from aqueous systems, Desalination 284 (2012) 167–174.
[200] S. Parvate, J. Singh, P. Dixit, J.R. Vennapusa, T.K. Maiti, S. Chattopadhyay,
Titanium dioxide nanoparticle-decorated polymer microcapsules enclosing phase
change material for thermal energy storage and photocatalysis, ACS Appl. Polym.
Mater. 3 (4) (2021) 1866–1879.
[201] A. Torres-Knoop, A. Poursaeidesfahani, T.J. Vlugt, D. Dubbeldam, Behavior of the
enthalpy of adsorption in nanoporous materials close to saturation conditions,
J. Chem. Theor. Comput. 13 (7) (2017) 3326–3339.
[202] T. Belova, Adsorption of heavy metal ions (Cu2þ, Ni2þ, Co2þ and Fe2þ) from
aqueous solutions by natural zeolite, Heliyon 5 (9) (2019), e02320.
[203] L.V.A. Gurgel, L.F. Gil, Adsorption of Cu (II), Cd (II) and Pb (II) from aqueous
single metal solutions by succinylated twice-mercerized sugarcane bagasse
functionalized with triethylenetetramine, Water Res. 43 (18) (2009) 4479–4488.
[204] V.C.G. dos Santos, C.A. de Toledo Gomes, D.C. Dragunski, L.A.D. Koslowski,
K. Lunelli, Removal of metals ions from aqueous solution using modified
sugarcane bagasse, Revista Virtual de Química 11 (4) (2019).
[205] A.D. Adamu, D.B. Adie, C.A. Okuofu, A. Giwa, Application of activated carbon
prepared from sugarcane bagasse for lead removal from wastewater, ATBU J. Sci.
Technol. Edu. 6 (3) (2018) 126–140.
[206] C. Mangwandi, T.A. Kurniawan, A.B. Albadarin, Comparative biosorption of
chromium (VI) using chemically modified date pits (CM-DP) and olive stone (CM-
OS): kinetics, isotherms and influence of co-existing ions, Chem. Eng. Res. Des.
156 (2020) 251–262.
[207] A. Tursi, A review on biomass: importance, chemistry, classification, and
conversion, Biofuel Res. J. 6 (2) (2019) 962–979, https://doi.org/10.18331/
brj2019.6.2.3.
[208] A.M. Yeneneh, S. Maitra, U. Eldemerdas, Study on biosorption of heavy metals by
modified lignocellulosic waste, J. Appl. Sci. 11 (21) (2011) 3555–3562, https://
doi.org/10.3923/jas.2011.3555.3562.
[209] A.A. Mosa, A. El-Ghamry, H. Al-Zahrani, E.M. Selim, A. El-Khateeb, Chemically
modified biochar derived from cotton stalks: characterization and assessing its
potential for heavy metals removal from wastewater, Env Biodiv Soil Security 1
(2017) 13, https://doi.org/10.21608/jenvbs.2017.956.1002.
[210] C. Patra, R.M.N. Medisetti, K. Pakshirajan, S. Narayanasamy, Assessment of raw,
acid-modified and chelated biomass for sequestration of hexavalent chromium
from aqueous solution using Sterculia villosa Roxb. shells, Environ. Sci. Pollut.
Res. Int. 26 (23) (2019) 23625–23637, https://doi.org/10.1007/s11356-019-
05582-4.
[211] F. Ghorbani, S. Kamari, S. Zamani, S. Akbari, M. Salehi, Optimization and
modeling of aqueous Cr(VI) adsorption onto activated carbon prepared from sugar
beet bagasse agricultural waste by application of response surface methodology,
Surf. Interf. 18 (2020) 100444, https://doi.org/10.1016/j.surfin.2020.100444.
19
Current Research in Green and Sustainable Chemistry 4 (2021) 100188
[212] D.D.F. Tomul, E. Kendüzler, Y. Arslan, B. Kabak, K. Demir, Determination of
adsorption characteristics of orange peel activated with potassium carbonate for
chromium(III) removal, J. Turkish Chem. Soc. A: Chemistry (2017) 1057–1070,
https://doi.org/10.18596/jotcsa.319791.
[213] M. Om Prakash, G. Raghavendra, S. Ojha, M. Panchal, Characterization of porous
activated carbon prepared from arhar stalks by single step chemical activation
method, Mater. Today: Proceedings 39 (2021) 1476–1481, https://doi.org/
10.1016/j.matpr.2020.05.370.
[214] K. Kante, C. Nieto-Delgado, J.R. Rangel-Mendez, T.J. Bandosz, Spent coffee-based
activated carbon: specific surface features and their importance for H2S separation
process, J. Hazard Mater. 201–202 (2012) 141–147, https://doi.org/10.1016/
j.jhazmat.2011.11.053.
[215] M. Sevilla, N. Diez, A.B. Fuertes, More sustainable chemical activation strategies
for the production of porous carbons, ChemSusChem 14 (1) (2021) 94–117,
https://doi.org/10.1002/cssc.202001838.
[216] J. Ouyang, L. Zhou, Z. Liu, J.Y.Y. Heng, W. Chen, Biomass-derived activated
carbons for the removal of pharmaceutical mircopollutants from wastewater: a
review, Separ. Purif. Technol. 253 (2020) 117536, https://doi.org/10.1016/
j.seppur.2020.117536.
[217] K. Ukanwa, K. Patchigolla, R. Sakrabani, E. Anthony, S. Mandavgane, A review of
chemicals to produce activated carbon from agricultural waste biomass,
Sustainability 11 (22) (2019) 6204, https://doi.org/10.3390/su11226204.
[218] LabChem, Sodium Hydroxide Safety Data Sheet, vol. 77, 2012, 9.
[219] A. Villabona-Ortiz, C. Tejada-Tovar, A. Herrera-Barros, A. Gonzalez-Delgado,
J. Nunez-Zarur, Preparation of biosorbents from corn residual biomass and its
application for Cr (VI) uptake, Contemp. Eng. Sci. 11 (29) (2018) 1401–1409,
https://doi.org/10.12988/ces.2018.83130.
[220] M.I. Din, S. Ashraf, A. Intisar, Comparative study of different activation treatments
for the preparation of activated carbon: a mini-review, Sci. Prog. 100 (3) (2017)
299–312, https://doi.org/10.3184/003685017X14967570531606.
[221] J.P. Chen, S. Wu, K.-H. Chong, Surface modification of a granular activated carbon
by citric acid for enhancement of copper adsorption, Carbon 41 (10) (2003)
1979–1986, https://doi.org/10.1016/s0008-6223(03)00197-0.
[222] H. Zhang, J. Shao, S. Zhang, X. Zhang, H. Chen, Effect of phosphorus-modified
biochars on immobilization of Cu (II), Cd (II), and as (V) in paddy soil, J. Hazard
Mater. 390 (2020) 121349, https://doi.org/10.1016/j.jhazmat.2019.121349.
[223] A.M. Yeneneh, M. Thanabalan, U.M.N.E. Demerdash, Biosorption of heavy metals
by potassium hydrogen phosphate and sodium oxalate modified lignocellulosic
waste, IEEE 6 (2011).
[224] W.-J. Liu, F.-X. Zeng, H. Jiang, X.-S. Zhang, Adsorption of lead (Pb) from aqueous
solution with Typha angustifolia biomass modified by SOCl2 activated EDTA,
Chem. Eng. J. 170 (1) (2011) 21–28, https://doi.org/10.1016/j.cej.2011.03.020.
[225] S.M. Abegunde, K.S. Idowu, O.M. Adejuwon, T. Adeyemi-Adejolu, A review on the
influence of chemical modification on the performance of adsorbents, Res.
Environ. Sustain. (2020).
[226] J.O. Ighalo, K.O. Iwuozor, C.A. Igwegbe, A.G. Adeniyi, Verification of pore size
effect on aqueous-phase Adsorption kinetics: a case study of methylene blue,
Colloid. Surface. Physicochem. Eng. Aspect. 626 (2021) 127119, https://doi.org/
10.1016/j.colsurfa.2021.127119.
[227] K.O. Iwuozor, J.O. Ighalo, E.C. Emenike, C.A. Igwegbe, A.G. Adeniyi, Do
Adsorbent Pore Size and Specific Surface Area Affect the Kinetics of Methyl
Orange Aqueous Phase Adsorption?, 2021.
[228] M. Tuzen, A. Sarı, Biosorption of selenium from aqueous solution by green algae
(Cladophora hutchinsiae) biomass: equilibrium, thermodynamic and kinetic
studies, Chem. Eng. J. 158 (2) (2010) 200–206.
[229] I. Anastopoulos, I. Pashalidis, A. Hosseini-Bandegharaei, D.A. Giannakoudakis,
A. Robalds, M. Usman, et al., Agricultural biomass/waste as adsorbents for toxic
metal decontamination of aqueous solutions, J. Mol. Liq. 295 (2019) 111684.
[230] D. Pathania, A. Srivastava, Advances in nanoparticles tailored lignocellulosic
biochars for removal of heavy metals with special reference to cadmium (II) and
chromium (VI), Environ. Sust. (2020) 1–14.
[231] K.O. Iwuozor, L.A. Ogunfowora, I.P. Oyekunle, Review on sugarcane-mediated
nanoparticle synthesis: a green approach, SugarTech (2021), https://doi.org/
10.1007/s12355-021-01038-7. Accepted Manuscript.