Biosorption of Heavy Metals From Aqueous Solution

Journal of Water Process Engineering 46 (2022) 102446
Contents lists available at ScienceDirect
Journal of Water Process Engineering

journal homepage: www.elsevier.com/locate/jwpe
Biosorption of heavy metals from aqueous solution by various chemically

modified agricultural wastes: A review
Hina Iqbal Syeda a, *, Ibrahim Sultan b, Kamal Seyed Razavi c, Pow-Seng Yap d, *
a
Faculty of Science, Engineering and Built Environment, Deakin University, Victoria 3216, Australia
b
School of Engineering, IT and Applied Sciences, Federation University, Victoria 3350, Australia
c
School of Science, Psychology and Sport, Federation University, Victoria 3350, Australia
d
Department of Civil Engineering, Xi'an Jiaotong-Liverpool University, Suzhou 215123, China
A R T I C L E I N F O A B S T R A C T
Keywords: In recent years, with the global increase in industrialization, there has been a significant increase in the amount
Adsorption of toxic pollutants such as heavy metals being released into water bodies. Adsorption is considered as one of the
Cost analysis most attractive methods due to its high efficiency and ability to remove heavy metals even at low concentration.
Kinetics and isotherms
Agricultural wastes-based biosorbents have attracted great interest due to their capability to effectively remove
Regeneration
Wastewater treatment
heavy metals from wastewater. Chemical modifications on biosorbents can significantly improve the biosorption
capacities and the longevity of the biosorbents. Most of the adsorption studies followed the Langmuir and
Freundlich adsorption isotherm models. The pseudo-second-order kinetic model best fitted most of the adsorp
tion kinetic studies. Moreover, ion exchange, electrostatic attraction and chelation were the governing adsorp
tion mechanisms in most of the studies. The adsorption process was usually spontaneous and endothermic in
nature. The regeneration of biosorbents was most effective when acids were used as eluents and this had allowed
some biosorbents to be reused efficiently up to 10 times. To elucidate a practical perspective, analysis on column
studies, adsorption performance using industrial wastewater, and cost analysis had been conducted. Cost analysis
proved that agricultural wastes-based biosorbents are cheaper than traditional adsorbents such as activated
carbon.
1. Introduction environment [4]. Industrial wastewater consists of various types of

contaminants which is why various pre-treatment steps are performed
Over the last few decades, there has been a dire need to solve the before the heavy metals can be targeted for removal [6]. Generally,
problem of heavy metal pollution in water. Heavy metals are extremely heavy metal removal technology falls into the tertiary treatment cate
toxic metallic elements that end up in the environment due to anthro gory [7].
pogenic activities. Industries such as mining, metal processing, fertilizer Over the years, various chemical, biological and physical technolo
industry, tanneries, etc. are some of the major sources of heavy metal gies have emerged as a result of the need to eliminate pollutants from
contamination [1]. Heavy metals can be present in the environment in wastewater [8]. Some examples of these technologies are ion exchange,
dissolved or particulate phase. The dissolved form is known to be more nanofiltration, ozonation, floatation, membrane technology, coagula
hazardous [2]. Heavy metal pollution adversely affects the health of tion, chemical precipitation and nanotechnology [4,9–13]. However,
humans, animals, soil and aquatic life [3]. They can easily disrupt the these technologies have certain disadvantages such as low removal ef
food chain due to their ability to accumulate in living cells and organs ficiency, secondary sludge production, disposal issues and expensive
[4]. Properties of heavy metals such as their non-biodegradability, operational costs [4,14,15]. Adsorption is a powerful technology that
mobility and persistence make these elements very harmful [5,6]. The has gained a lot of attention over the other technologies for heavy metal
atomic structure and the electron shells of these elements attribute to removal [6,16,17]. This process has several advantages such as the
their highly reactive nature and ability to perform physiochemical and ability to treat heavy metals that are present in low concentration
biochemical activities, and thus may result in deleterious effects on the (1–100 mg/L), low operational costs and regeneration ability [8,18].
* Corresponding authors.
E-mail addresses: hinaiqbs@gmail.com (H.I. Syeda), PowSeng.Yap@xjtlu.edu.cn (P.-S. Yap).
https://doi.org/10.1016/j.jwpe.2021.102446
Received 2 October 2021; Received in revised form 5 November 2021; Accepted 7 November 2021
Available online 13 January 2022
2214-7144/© 2021 Elsevier Ltd. All rights reserved.
H.I. Syeda et al. Journal of Water Process Engineering 46 (2022) 102446
Various types of adsorbent materials including natural, biological and Table 1

waste-based adsorbents have been evaluated for heavy metal removal of Common heavy metals, their sources, effects on human health and maximum
which activated carbon is widely used commercially [19]. Activated contamination limit (MCL) according to United States Environmental Protection
carbon is very efficient in removing heavy metals but is generally very Agency (USEPA).
expensive due to its production cost which includes an energy- Heavy Health toxicity Source/products MCL Reference
consuming and high temperature carbonization process [20]. Owing metals (mg/L)
to this drawback, researchers over the last few decades have been paying Chromium Skin ulcers, cancer, Stainless steel, 0.05 [40,41]
more attention to cost-effective and efficient adsorbents that can be liver and kidney electroplating,
produced from inexpensive biomass. damage cement, rubber.
Lead Miscarriages in Fossil fuel 0.006 [40–42]
Agricultural wastes are a category of biomass that are abundantly pregnant women, burning, mining,
available in the environment and have the ability to efficiently adsorb anemia, congenital manufacturing,
heavy metals on their surface effectively [1,14,21–25]. The surface paralysis, gasoline,
characteristics of these biosorbents such as availability of metal binding gastrointestinal automobile
damage emissions
functional groups and a highly porous area aid in entrapping heavy
Nickel Birth defects, Industrial dusts, 0.20 [41–43]
metal ions within their pores [19]. However, these agricultural based- chronic bronchitis, Aerosols.
biosorbents are required to undergo chemical modification to improve lung embolism,
the adsorption capacity, structural stability and reusability. Biosorbent larynx cancer, lung
modification can typically be divided into physical and chemical mod cancer.
Cadmium Lung cancer, Batteries, plastics, 0.01 [40–42]
ifications. Physical modification involves breaking down of adsorbents
bronchitis, bone metal coatings,
to desired sizes and gasification at high temperature with gases such as defects, renal pigments, nuclear
carbon dioxide [26,27]. A common physical modification method in dysfunction. fission plants.
volves surface activation by using nitrogen gas to produce activated Mercury Brain and kidney Thermometer, 0.00003 [40,41]
damage, damage in dental fillings,
carbon from the biosorbent [28]. On the other hand, while performing
developing fetus, bulbs, batteries,
chemical modification on a biosorbent, acids such as hydrochloric acid skin rashes, production of
[29] and nitric acid [29], alkalis such as sodium hydroxide [30] and increase in blood chlorine gas.
potassium hydroxide [31], salts such as calcium chloride [32] and po pressure and heart
tassium chloride [33] as well as other substances such as iron oxide, zinc rate.
Zinc Dizziness, Refineries, 0.80 [41,42,44]
oxide, copper oxide, methanol etc. are commonly used as modifying
vomiting, fatigue, plumbing, metal
agents [34,35]. The aim of this review article is to systematically review renal damage. plating.
the application of chemically modified agricultural wastes for the Arsenic Skin lesions, Metal smelter, 0.05 [40–42,45]
removal of heavy metals from water and wastewater. This review article neurological pesticides,
complications, fungicides.
provides the recent advances in the field by comprehensively covering
diabetes,
the adsorption performances of these biosorbents along with their un respiratory
derlying adsorption mechanisms and critical analysis of the effect of complications,
several important experimental parameters governing the adsorption carcinogen
process. The article also elucidates the practical aspects such as column Copper Stomach and Chemical industry, 0.25 [41,42,44]
intestinal irritation, metal piping,
studies, cost analysis, performance of biosorbents using real industrial
anemia, liver and wood
wastewater and desorption studies of various agricultural wastes which kidney damage preservatives,
are often neglected in biosorption studies. The inclusion of these topics is architecture.
to allow the readers to have a better understanding on what is pre
venting biosorbents to replace existing commercial adsorbents such as
ion exchange resin and activated carbon. In addition, recommendations the removal of heavy metals. Membrane filtration, chemical precipita
have been provided to enable lab-scale biosorption to be eventually tion, ion exchange, coagulation-flocculation, adsorption and electrodi
applied at industrial-scale. alysis are some examples of the technologies. However, most of these
techniques have limitations that make them inefficient [46].
2. Heavy metals and their harmful effects on human health
2.1.1. Membrane filtration
Heavy metals generally refer to metal and metalloids that have an Membrane filtration is a popular method used in industries to treat
pollutants in wastewater. It can treat organic compounds, suspended
atomic density greater than 4 g/cm3 which is 5 times greater than water
solids and inorganic compounds such as heavy metals. There are various
[36–38]. Some common heavy metals are arsenic, chromium, cadmium,
types of membranes such as ultrafiltration membranes, microfiltration
lead, copper, zinc, nickel, iron, and barium. The toxic behaviour of
membranes, nanofiltration membranes and reverse osmosis membranes.
heavy metals is exacerbated due to its inability to naturally degrade over
The type of membrane is chosen on the basis of the size of the pollutant
time. The accumulation of these heavy metals in plants, soil and aquatic
[41]. Although membrane filtration is effective, it has limitations such
life is a pathway to infiltrate the food chain. Heavy metal accumulation
in the human body can cause serious health issues such as cancer, as high initial cost, high maintenance cost, membrane fouling and
limited lifespan [46].
impaired growth and reproduction, neurological damage, permanent
brain damage, encephalopathy, and chronic damage to the nervous
2.1.2. Ion exchange
system [39].
Heavy metals are very harmful even at trace amounts. Therefore it is In this technique, an ion exchanger such as resins are used to remove
the desired ions by an exchange mechanism. The ion exchange material
a necessity to develop efficient methods for the removal of heavy metals
from wastewater. The most commonly found heavy metals in the envi is able to replace its cation with the heavy metal ion in the polluted
stream. Two examples of commonly used ion exchange resins are
ronment due to industrial pollution are provided in Table 1.
strongly acidic resins with sulfonic acid groups (− SO3H) and weakly
acid resins with carboxylic acid groups (− COOH) [47]. Although ion
2.1. Conventional methods for removal of heavy metals
exchangers are efficient in removing heavy metals, their capital and
operation cost are high [48].
Over the years, numerous technologies have been implemented for
2
2.1.3. Electrodialysis 3. Biosorption

This process involves the use of a semi-permeable ion exchange
membrane through which the heavy metal-polluted water is passed by 3.1. Biosorption and its principals
applying an electric potential. The membrane sheets are either cationic
or anionic in nature. In a positively or negatively charged ionic mem Biosorption is a physio-chemical process in which a biological ma
brane, the anions are directed towards the anode and the cations are terial is used for the removal of selected substances from an aqueous
directed towards the cathode [49]. solution [61]. Due to the growing demand of finding environmentally
friendly approaches towards pollutant removal, more attention is being
2.1.4. Chemical precipitation drawn towards ‘green chemistry’ or ‘sustainable chemistry’. Biosorption
In this method, the heavy metals ions react with a chemical to form is a process that complies with these guidelines. Some of the principles of
insoluble precipitates like hydroxides and sulphide precipitates. This can green chemistry are as follows [62]:
then be removed by sedimentation or filtration techniques [47]. The
operation of this process is simple but there is a large amount of sludge (1) Replace toxic chemical reagents
generation and this can increase the maintenance cost tremendously (2) Utilize safer reagents
[46]. (3) Avoid the generation secondary wastes that cannot be recycled
(4) Reuse reagents
2.1.5. Coagulation and flocculation (5) Reduce energy consumption
Coagulation and flocculation is a pH dependent process which in (6) Use techniques that are ecofriendly to detect analytes
volves the addition of coagulants such as ferric/alum salts. The process (7) Using automation and developments on a microscale level
destabilises the particle to cause sedimentation. After that, the size of the
unstable particle is increased by flocculating the particles into floccules. Biosorption falls under the category of adsorption with the difference
The drawbacks of this process include production of toxic sludge, heavy being that the adsorbent is made from a biological matrix. The sorption
use of chemicals and high operational costs [46,47]. process may include various mechanisms depending upon the type of
sorbate, the biosorbent being used and other environmental factors.
2.1.6. Adsorption Biosorption is a metabolically independent and physiochemical process
Adsorption is defined as a process in which ions and molecules are which may involve mechanisms such as ion exchange, chelation, elec
bonded onto a solid material [10,50–52]. Adsorbent surfaces are mostly trostatic interaction, adsorption, redox reactions, precipitation and
heterogeneous. The adsorption sites are occupied from the highest- surface complexation. The possible mechanisms of biosorption are
energy sites to the lowest energy sites [53]. The adsorption process depicted in Fig. 1. The biosorption process will continue until it reaches
creates a layer of adsorbate on the surface [54]. Adsorption process an equilibrium state [63]. This process has several advantages such as
mainly occurs in three steps. Firstly, the heavy metal from the bulk so using cost effective and sustainable materials, the process being meta
lution transfers to the adsorbents surface; secondly, the adsorption of the bolically independent, effectively usage of waste materials and high
heavy metal on the surface occurs and lastly, the heavy metals transport removal efficiency even at low heavy metal concentrations [64].
within the adsorbent [41]. Some of the factors that contribute to the Biosorbents can be classified as green adsorbents [21]. They can be
adsorption efficiency are pore volume, surface area, polarity, number of categorized into algae, microbial and agricultural wastes-based bio
active sites and functional groups [55]. Adsorption is one of the most sorbents. One of the major advantages of using dead biomass such as
commonly technology used for pollutant clean up in wastewater agricultural wastes as opposed to living biomass is that they do not
[47,52]. It is a very efficient process that is able to eliminate heavy require a growth media and nutrients for their maintenance which will
metals present at low concentrations, produce less sludge and maintain reduce the overall operational cost. The process will also allow easier
low operational cost [15,56,57]. Various types of adsorbent materials mathematical and statistical modelling of heavy metal uptake
have been used for the removal of heavy metals. They can be classified [55,63,65]. The fabrication of green adsorbents in general requires
into inorganic, bio-based, carbon-based and polymeric adsorbents [58]. lesser energy and can be recycled easily which reduces the overall waste
Some examples of commercially available adsorbents on the market are production [46].
activated carbon, silica gel and alumina [59]. Examples of different
types of adsorbents are presented in Table 2. Typically, an adsorbent 3.1.1. Steps involved in biosorption studies
material should be low cost, have good structural and mechanical sta Adsorption studies are generally conducted in the following steps:
bility, have high adsorption efficiency, have a large surface area and
have good regeneration capability. The most commonly used adsorbent 1. First, the biosorbent undergoes pre-treatment. This may include
material is activated carbon. This is because it has outstanding proper sieving, milling and washing.
ties such as large surface area and excellent adsorption ability. Although 2. Then, the biosorbent is physically or/and chemically modified to
it is very efficient for heavy metal removal, it is very costly. For instance, improve the availability of functional groups and active sites on the
regeneration process alone of spent activated carbon comprises of 75% biosorbent for maximum biosorption to take place.
of its operating cost in a fixed bed GAS operator [60]. Another issue with 3. The biosorbent is then characterized by using techniques such as
these adsorbent materials is the lack of satisfactory disposal systems. Scanning Electron Microscopy (SEM), Field Emission Scanning
Electron Microscopy (FESEM), Fourier Transform Infrared Spec
troscopy (FTIR), X-ray Diffraction (XRD), Transmission Electron
Table 2
Different categories of adsorbents and their examples [58].
Microscopy (TEM), and X-ray Photoelectron Spectroscopy (XPS)
analysis. Various experimental factors that affect biosorption include
Type of Examples of adsorbents
pH, temperature, adsorbent dose, metal concentration, contact time
adsorbents
and presence of competing ions. These factors are varied to find the
Inorganic Activated alumina, silica gel, metal oxides, metal hydroxides, optimum conditions for biosorption. After that, the amount of heavy
zeolites, clays, pillared clays.
Biobased Lignocellulosic residues, cellulose, nanocellulose, wood fibers,
metal adsorbed is measured through analytical techniques such as
jute fibers, sawdust. atomic absorption spectrometry (AAS) and Inductively Coupled
Carbon-based Activated carbon, mesocarbon, carbon nanotubes, molecular Plasma analysis (ICP).
carbon sieves, fullerenes.
Polymeric Ion exchange, resins, membrane, molecularly imprinted polymers
3
Fig. 1. Common mechanisms that occur in the biosorption of heavy metals (M+).
4. Adsorption kinetic and adsorption isotherm studies are conducted to 3.2.1. Ion exchange
determine the adsorption rates, adsorption equilibrium and Ion exchange is one of the most common mechanisms that takes
maximum adsorption capacity. place during the biosorption process. This reversible exchange process
5. Next, desorption is conducted to recover the heavy metals from the involves the electrostatic interaction between positively charged metal
wastewater and for the regeneration of the biosorbent material for ions in the solution with the negatively charged ions present on the
further study and use. surface of the biosorbent material. Typically, there are various func
tional groups and free sites available on the surface of the biosorbent
3.2. Mechanisms involved in the removal of heavy metals by agricultural material for this exchange to take place. In a study conducted by Qu
wastes in heavy metal removal et al. [70], the authors used sulphur functionalized rice husk for the
removal of cadmium from water. The authors reported that the main
Agricultural wastes are typically available in large quantities and can mechanisms involved were ion exchange and chelation. Upon con
easily be transformed into efficient heavy metal adsorbents [20]. These ducting EDX analysis for both modified and unmodified rice husks, it
wastes mainly consist of various types of inorganic and organic matter was found that the Na(I) ions increased from 4.33 mg/g to 20.55 mg/g
such as hemicellulose, cellulose, lignin, protein, carbohydrates, pectin and Mg(II) ions had increased from 0.02 mg/g to 0.93 mg/g after the
etc. in their cell wall [66]. The biosorption process of heavy metal on biosorption process had reached equilibrium which means that ion ex
agricultural wastes mostly is due to functional groups such as carboxyl, change process would have taken place between the heavy metal ions
amine and hydroxyl groups [23]. Agricultural wastes also contain and the positively charged magnesium and sodium ions. In another
different types of minerals and carbon content that are responsible to study, Feng et al. [32] studied the adsorption of copper, lead and zinc by
drive physical forces such as van der Waals forces, dipole-dipole inter using modified orange peel. They found that the mechanism of heavy
action, hydrophobicity, steric interaction and hydrogen bonding [67]. metal uptake by the modified orange peel is based on the ion exchange
In order to understand the mechanism of heavy metal adsorption in mechanism between the copper, lead, zinc ions and the calcium chelated
biosorbents, the functional groups present on the biosorbent surface onto the carboxylic groups present in the structure of pectin. Similarly,
must be analysed [50]. The interactions between metal ions and func Reddad et al. [71] also reported that ion exchange mechanism and
tional groups need to be studied for a better understanding of the bio chelation were the main mechanisms that took place between Pb2+,
sorption process. Agricultural wastes generally consist of various Cu2+, and Zn2+on sugar beet pulp with the calcium ions.
functional groups such hydroxyl group (present in alcohol and carbo
hydrates), carboxyl (present in fatty acids, protein and organic acids), 3.2.2. Complexation
ester (found in lipids), keto group, aldehyde and amine groups (found in Functional groups present in the biosorbent have the ability to form
nuclei acids and proteins) etc. [11,68]. These functional groups aid in complex coordinate bonds with heavy metals ions. A complex com
binding metal cations and anions by forming coordinate complexes [23]. pound can be defined as a poly-atomic molecule that has one or more
The biosorbents generally have large surface area, are very porous and central atoms, surrounded by and attached to ligands [72]. For example,
consists of ligands. These characteristics make agricultural based-bio in a study conducted by Harripersadth et al. [73], the authors reported
sorbents desirable for adsorption [19]. Various mechanisms including that complexation was the main mechanism for the removal of cadmium
complexation, ion exchange, chelation, precipitation, and physisorption and lead ions using sugarcane bagasse and eggshells as a biosorbent
can be involved in the metal ion uptake process [69]. The biosorption material. The authors explained through FTIR analysis that the carboxyl
process is greatly affected by factors such as pH, adsorbent dose, tem groups present in eggshells form complexes with cadmium and lead
perature, metal ion concentration, ionic strength, reaction time and ions. For sugarcane bagasse, FTIR analysis confirmed the presence of
sorbent size. Therefore, it is necessary to study the effects of these pa hydroxyl, carbonyl and aromatic rings. These functional groups donate
rameters on the biosorption capacity. Some of the commonly occurring an electron pair to be able to form complexes with the metal ions.
biosorption mechanisms occurring during sorption of heavy metals on
biosorbents are discussed below. 3.2.3. Chelation
When a ligand is attached to the central atom through two or more
coordinating atoms, then the complex is called chelate [72,74] and the
4
chelate formation process is known as chelation. Biosorbents generally equilibrium (mg/L), qe is the mass of metal ions adsorbed at equilibrium
contain ligands that assist the chelation process. For example, He et al. (mg/g), KF is the adsorption capacity constant (mg/g)(L/mg)1/n, n is a
[75] used a lignin-based biosorbent derived from corn for the removal constant denoting the degree and favourability of adsorption.
and recovery of Au(III) from aqueous solution. The authors reported that For instance, in a study conducted by Edathil et al., [87] the authors
the adsorption process took place because Au (III) ions chelated onto the fitted the adsorption data into the Langmuir, Freundlich, Dubinin-
biosorbent through the nitrogen-containing functional groups from Radushkevich and Temkin models to study the adsorption of lead ions
polyaniline and oxygen-containing functional groups from lignin which on a magnetic coffee waste nanocomposite. The Langmuir isotherm best
was enzymatically hydrolysed. Following this, after a redox reaction fitted the experimental data with an R2 value greater than 0.99. This
between the functional groups and the Au(III) ions, Au(III) was con indicates that a monolayer adsorption took place during the adsorption
verted into Au(0). process. The maximum adsorption capacity was 41.15 mg/g at optimal
experimental conditions.
3.2.4. Micro-precipitation
In this process, an insoluble metal particulate is formed. It is another 4.2. Adsorption kinetics
common process that may occur during the adsorption of heavy metals.
During micro-precipitation, precipitation takes place on the surface of In an adsorption process, adsorption kinetic studies are used to
the biosorbent or within the pores of the adsorbent. For example, Liu describe the mechanisms of reaction rate control such as progress of
et al. [76] used water-melon rind as a biosorbent to adsorb copper, zinc chemical reactions processes and mass transfer. These models describe
and lead from aqueous solution. The mechanisms involved in the the rate of solute bonding on the surface of the biosorbent. The most
adsorption were ion-exchange and micro precipitation. The SEM mi commonly used kinetic models are pseudo-first-order and pseudo-
crographs and analysis in the study revealed that upon interaction be second-order kinetic models. These models assume that the rate of
tween the biosorbent and the heavy metal, the pores on the surface sorption is proportional to the number of free sites on the surface of the
became less as they were occupied by the metal ions. The active surface sorbent in the proper power (first or second) [50]. In Table 4, various
area also increased and was covered by the metal ions that had adsorption studies using agricultural wastes have been listed along with
precipitated. Panda et al. [77] also reported micro-precipitation as a the best fitting kinetic model, coefficient correlation R2 value, experi
mechanism through which cadmium ions were adsorbed on the Lathyrus mental conditions such as contact time (CT), equilibrium contact time
sativus husk. (Te), temperature (T), initial metal ion concentration (Co), dosage (D),
pH and equilibrium adsorption capacities (qe). As seen in Table 4, most
4. Adsorption studies of the adsorption studies fit best in the pseudo-second-order kinetic
model. This means that the adsorption mechanism is mainly dominated
4.1. Adsorption isotherms by chemisorption. The mathematical equation for the pseudo-second-
order kinetics is as follows:
To gain a better understanding on the mechanism of adsorption be
t 1 t
tween the adsorbate and adsorbent, various mathematical models = + (3)
qt k2 q2e qe
known as adsorption isotherms are applied to the system. The different
types of adsorption isotherms include Langmuir, Freundlich, Dubinin- In this equation, qe and qt is the adsorption capacities (mg/g) at
Radushkevich, Sips, Halsey, Temkin, Redlich-Peterson etc. [78–84]. In equilibrium and time (t), k2 is the rate constant for second-order
Table 3, various adsorption studies have been listed along with the best adsorption (gmg− 1 min− 1) and is determined from the linear plot of t/
fitting adsorption isotherm model, coefficient correlation R2 value, qt versus t.
experimental conditions such as contact time (CT), equilibrium contact For instance, Owalude and Tella [113] studied the adsorption ki
time (Te), temperature (T), initial metal ion concentration (Co), dosage netics of hexavalent chromium on modified groundnut hull by studying
(D), pH and the calculated maximum adsorption capacity qmax. As seen the uptake of the hexavalent chromium ions at different time intervals
in Table 3, most of the studies fit in best with either the Langmuir or and at optimal conditions. The experimental data on the effect of contact
Freundlich isotherm models. The conceptual basis of the Langmuir time on the adsorption of hexavalent chromium ions was fitted in the
isotherm model is that the biosorption takes place in a monolayer sur pseudo-first-order and pseudo-second-order kinetic models. The kinetics
rounding a homogenous solid surface in which there is no contact be data fitted best into the pseudo-second-order adsorption kinetic model
tween the adsorbed species [85]. The Freundlich isotherm suggests the with R2 value of 0.9992 indicating that the governing adsorption
heterogeneity of the adsorbate [86]. The mathematical equations for the mechanism was chemisorption involving valence forces through ex
Langmuir isotherm is as follows [78]: change and/or sharing of electrons between the adsorbent and adsor
bate [30].
Ce Ce 1
= + (Linear) (1)
qe qm qm KL
5. Brief overview of chemical modifications of biosorbents for
qe = qm KL Ce (non − linear) (2) the removal of heavy metals
1+KL Ce
In the above equation, Ce is the aqueous phase adsorbate equilibrium 5.1. Chemical modifications of agricultural wastes
concentration (mg/L), qm is the theoretical maximum monolayer
coverage capacities (mg/g), KL is Langmuir isotherm constant (L/mg) Depending on the genetic makeup of agricultural wastes, the
and qe is the equilibrium adsorption capacity (mg/g). The Freundlich adsorption capacity may not be high because of low mechanical strength
isotherm model can be described with the following mathematical or lack of preferential active sites for adsorption. Moreover, in some
equation [79]: cases, raw biosorbents may contain substance that may block functional
groups present on the surface and thereby hinder biosorption leading to
logCe reduced adsorption capacity [140]. Therefore, over the years re
logqe = logKF + (linear equation) (3)
n searchers have been developing ways to enhance adsorption capacity,
active sites for adsorption, mechanical strength and longevity of bio
(4)
1
qe = KF Ce n (non − linear equation)
sorbents through various physical, biological and chemical modifica
In the above equation, Ce is the concentration of metal ions at tions [141]. However, chemical modification of biosorbents often takes
precedence over other forms of treatment due to its simplicity and
5
Table 3
Adsorption isotherms for various agriculture waste based adsorbents.
Biosorbent Metals Maximum removal % Conditions R2 Adsorption isotherm model Reference
removed (mg/g) Removal
Coffee waste Pb2+ 41.15 – T = 25 ◦ C 0.991 Langmuir [87]

Co = 0–100 mg/L
CT = 240 min
Te = 30 min
pH = 7.3
Orange peel Pb2+ 476.1 – CT = 3 h 0.9964 Langmuir [88]
Cd2+ 293.3 Te = 150 min 0.9886
Ni2+ 162.6 D = 2 g/L 0.9926
T = 30 ◦ C
pH = 5.5
Co = 50–1200 mg/L
Orange peel Cd2þ 13.7 – T = 25 ◦ C Langmuir Langmuir [89]
Cu2+ 15.27 pH = 5 Cd2þ = 0.97 Freundlich
Pb2+ 73.53 Co = 100–600 mg/L Cu2+ =
CT = 120 min 0.998
Pb2+ = 0.99
Freundlich
Cd2þ = 0.96
Cu2+ = 0.97
Pb2+ = 0.96
Banana peel Cr(VI) 6.1728 96 pH = 3 0.997 Freundlich Langmuir [85]
0.9884
2+
Banana peel Mn 5.7306 94 pH = 8 0.999 Langmuir [90]
T = 25 ◦ C
Orange peel Pb2+ 164 – T = 30 ◦ C 0.982 Langmuir [91]
Zn2+ 80 pH = 5 0.919
Dosage = 5 g/L
Co = 25–800 mg/L
Contact time = 2 h
Orange peel Cu2+ 70.73 – pH (Cu2+) = 5 0.9922 Langmuir [32]
Pb2+ 209.8 pH (Pb2+) = 5.5 0.9948
Zn2+ 56.18 pH (Zn2+) = 5.5 0.9910
Contact time = 12 h
D = 4 g/L
Litchi peels Pb2+ 78.74 – Contact time = 3 h 0.99 Langmuir [92]
T = 25 ◦ C
D = 5 g/L
pH = 6.0
Co = 50–240 mg/L
Pineapple peel Cd2+ 42.10 – Co = 50–250 mg/L 0.9839 Langmuir [93]
Pb2+ 28.55 T = 25 ◦ C 0.9916
pH = 4
Dose = 4 g/L
Lemon peel Ni2+ 36.74 – pH = 5, 0.992 Langmuir [94]
D = 5 g/L
T = 25 ◦ C
Co = 5–500 mg/L
Banana peel Pb2+ 89.286 – pH (Pb2+) = 7 0.9964 Langmuir [95]
Cu2+ 5.720 pH (Cu2+) = 9 0.9994
Papaya leaves Pb2+ 284.35 – pH = 4 0.9188 Freundlich [96]
Petai peel Pb2+ 36.01 – pH = 5 0.9955 Langmuir [96]
Banana peel Cd2+ 27.77 – Co = 0–80 mg/L 0.978 Langmuir [97]
Cr3+ 38.46 pH = 6
Zn2+ 9.52 T = Room temperature
Kiwi Cd2+ 15.87 – Co = 0–80 mg/L 0.979 Langmuir [97]
Cr3+ 41.66 pH = 6
Tangerine Cd2+ 17.54 – Co = 0–80 mg/L 0.983 Langmuir [97]
Cr3+ 47.61 pH = 6
Tomato waste Pb2+ 152 – D = 0.1 g 0.985 Freundlich [98]
Te = 90 min
pH = 4
Peanut husk Cd2+ 7.68 – Te = 60 min 0.999 Langmuir [99]
Pb2+ 28.3 D = 4 mg/mL 0.999
Peanut husk Ni2+ 0.1473 – pH = 6.5 0.9921 Langmuir, Langmuir–Freundlich and [100]
Dosage = 2.5 g/L 0.9961 Redlich–Peterson
Te = 30–60 min 0.9947
Peanut husk Cr(VI) 33.11 – CT = 24 h 0.998 Freundlich [101]
T = 293 K
D = 100 g
Sugarcane Cd2+ 33.2 – Co (Cd2+) = 0–100 mg/L – Freundlich [102]
bagasse Pb2+ 116.7 Co (Cd2+) = 0–500 mg/L
(continued on next page)
6
Table 3 (continued )
CT = 4 h
T = 25 ◦ C
Sugarcane Zn2+ – 74.91 Co = 20–100 mg/L 0.9953 Freundlich [103]
bagasse Cr(IV) 76.54 CT = 120 min 0.9894
D = 0.9 g
T = 30 ◦ C
pH = 6
Sugarcane Pb2+ 52.63 – Co = 100–1000 mg/L 0.989 Langmuir [104]
bagasse CT = 24 h
Sugarcane Pb2+ 30.68 – Co = 100–1000 mg/L 0.983 Langmuir [104]
bagasse CT = 24 h
2+
Sugarcane Pb 35.09 – Co = 100–1000 mg/L 0.995 Langmuir [104]
bagasse CT = 24 h
Sugarcane Pb2+ 7.297 – pH = 5 0.992 Langmuir [105]
bagasse T = 25 ◦ C
CT = 120 min
Sugarcane Cd2+ 2.137 – CT = 3 h 0.99 Langmuir [29]
bagasse Cr2+ 6.782 D=1g 0.99
Pb2+ 21.242 Co = 0–400 μg/mL 0.99
T = 25 ◦ C
bagasse Cr2+ 5.393 D=1g 0.94
Pb2+ 18.724 Co = 0–400 μg/mL 1.0
T = 25 ◦ C
bagasse Cr2+ 5.122 D=1g 0.99
Pb2+ 23.251 Co = 0–400 μg/mL 1.0
T = 25 ◦ C
Wheat straw Cd2+ 3.075 – CT = 3 h 1.0 Langmuir [29]
Cr2+ 7.550 D=1g 0.99
Pb2+ 21.237 Co = 0–400 μg/mL 0.98
T = 25 ◦ C
Cr2+ 6.677 D=1g 1.0
Pb2+ 22.398 Co = 0–400 μg/mL 0.99
T = 25 ◦ C
Cr2+ 6.081 D=1g 1.0
Pb2+ 18.345 Co = 0–400 μg/mL 0.99
T = 25 ◦ C
Wheat straw Pb2+ 50.76 – pH = 5 0.999 Langmuir [35]
D = 4 g/L
CT = 30 min
Sugarcane As(III) 28.57 – Te = 120 min 0.974 Langmuir [106]
bagasse As(V) 34.48 pH = 7 0.977 Freundlich
Sugarcane As(V) 22.1 – pH = 4 0.99 Langmuir [107]
bagasse CT = 3 h
T = 22 ◦ C
D = 0.25 g
Sugarcane Co2+ 56.1 – Cobalt 0.9658 Langmuir [108]
bagasse Cu2+ 93.5 pH = 5.75 0.9388
Ni2+ 93.2 D = 0.2 g/L 0.9800
T = 25 ◦ C
Te = 120 min
Copper
pH = 5.5
D = 0.2 g/L
T = 25 ◦ C
Te = 120 min
Nickle
pH = 5.75
D = 0.2 g/L
T = 25 ◦ C
Te = 120 min
Rice husk Ni2+ 26.6 63.57 T = 25 ◦ C 0.96 Langmuir [109]
CT = 24 h 0.98 Freundlich
Co = 20–90 mg/L
D=1g
pH = 7
Rice husk Cd2+ 45.5 – pH = 4 0.997 Langmuir [110]
Ni2+ 55.5 Te = 45 min 0.993
T = 25 ◦ C
Rice husk Cd2+ 137.16 – T = 288 K 0.9999 Langmuir [70]
D = 0.5 g/L
Co = 10–250 mg/L
7
CT = 120 min
pH = 7
Cashew nut shell Cu2+ 48.05 – Co = 20–100 mg/L 0.9643 Freundlich [111]
D = 2 g/L
pH = 6
Cashew nut shell Pb2+ 8.30 – Co = 10–50 mg/L 0.9997 Langmuir [112]
CT = 30 min
Groundnut hull Cr(VI) 131 – T = 28 ◦ C 0.993 Freundlich [113]
pH = 2
CT = 60 min
D=2g
Co = 13 mg/L
Citrus lemon peels U(VI) 24.39 – pH = 8 0.963 Langmuir [114]
T = 25.0 ± 0.5 ◦ C
Garlic peel Pb2+ 109.05 – pH = 5 0.99 Langmuir [115]
CT = 120 min
Musk melon peel Pb2+ 167.8 – pH = 4.5 0.9938 Langmuir [116]
T = 25 ◦ C
CT = 120 min
D = 0.080 g
Grapefruit peel Cr(VI) 39.0628 – Co = 15–100 mg/L 0.9802 Langmuir [117]
CT = 24 h
pH = 5.5
Grapefruit peel Pb2+ 12.73 – pH = 5.3–6.5 0.9827 Freundlich [118]
CT = 1.5 h
D = 10 g/L
Co = 100 mg/L
T = 30 ◦ C
Grapefruit peel Cd2+ 42.09 – CT = 300 min 0.924 Freundlich [119]
Ni2+ 46.13 Co = 10–200 mg/L 0.984
CT = 120 min
pH = 5
D = 4 g/L
Cucumber peel Cd2+ 0.998* – Co = 20–300 mg/L 0.998 Langmuir [120]
pH = 4
T = 30 ◦ C
D = 0.1 g
Lemon peel Co2+ 35.71 – D = 2 g/L 0.998 Langmuir [121]
pH = 6
CT = 6 h
T = 30 ◦ C
Orange peel Cu2+ 59.77 – Te = 20 min 0.992 Langmuir [33]
CT = 1.5 h 0.977 Freundlich
D = 50 mg
pH = 5–5.5
Orange peel Cd2+ 125.63 – Te = 20 min 0.996 Langmuir [33]
D = 50 mg
pH = 5–5.5
Orange peel Pb2+ 141.84 – Te = 20 min 0.999 Langmuir [33]
CT = 1.5 h
D = 50 mg
pH = 5–5.5
Orange peel Zn2+ 45.29 – Te = 20 min 0.998 Langmuir Freundlich [33]
CT = 1.5 h 0.993
D = 50 mg
pH = 5–5.5
Orange peel Ni2+ 49.14 – Te = 20 min 0.973 Langmuir [33]
D = 50 mg
pH = 5–5.5
Orange peel Pb2+ 164 – D = 50 mg 0.982 Langmuir [91]
Zn2+ 80 Co = 25–800 mg/L 0.919
pH = 5
Orange peel Cr(VI) 7.44 – D = 25 mg 0.99055 Langmuir [122]
Co = 10 and 50 mg/L
pH = 1
CT = 1 h
Orange peel Cu2+ 40.37 – T = 25 ◦ C 0.996 Langmuir [123]
CT = 2 h
pH = 5.3
D = 5 g/L
Orange peel Cu2+ 59.77 – T = 25 ◦ C 0.992 Langmuir [123]
CT = 2 h
8
pH = 5.3
D = 5 g/L
Orange peel As(V) 43.69 95 pH = 5.5 – Langmuir [124]
T = 25 ◦ C
2+
Cassava peel Hg – 72.98 T = 25 ◦ C – Freundlich [125]
pH = 6
D = 0.5 g
Te = 240 min
Lemon peel Hg2+ – 49.83 T = 25 ◦ C – Freundlich [125]
pH = 6
D = 0.5 g
Te = 330 min
Corncob Pb2+ 0.0381* – pH = 5 0.9965 Langmuir [126]
0.2095* D = 200 mg 0.9902
CT = 60 min
T = 298 K
Co = 0.1–2.0 mmol/L
Peanut hull Ni2+ 8.63 – T = 25 ◦ C 0.9957 Langmuir [127]
Co = 25 mg/L,
D = 4 g/L
pH = 6
Banana peel Pb2+ 90 – pH = 5 0.950 Freundlich [30]
D = 0.5 g
CT = 12 h
Green tea waste As(III) 0.4212 – D = 0.3 g 0.9523 Langmuir [128]
T = 33 ◦ C
pH = 3
Green tea waste Ni2+ 0.3116 – D = 0.3 g 0.9262 Freundlich [128]
T = 33 ◦ C
pH = 3
Coconut pith Ni2+ 24.39 – pH = 6 0.994 Langmuir [129]
D = 2 g/L
Co = 50 mg/L
CT = 120 min
Tea waste U(III) 111.61 – T = 298 K 0.9682 Langmuir [130]
pH = 5
D = 0.5 g/L
Co = 10 mg/L
Tea waste U(VI) 104.95 – T = 298 K 0.9892 Langmuir [130]
pH = 5
D = 0.5 g/L
Co = 10 mg/L
Tea waste Pb2+ 153 – pH = 6 0.993 Langmuir [131]
Cd2+ 222 0.963
Tea waste Ni2+ 38.3 – pH = 4 0.975 Langmuir [132]
T = 323 K
2+
Corn cob + petai Pb 2.230 – Co = 400 mg/L 0.961 Langmuir [133]
hull
Watermelon rind As(V) – 98 Co = 4 mg/L 0.98 Langmuir [134]
As(III) 99 pH (As(III)) = 8.2 0.99
pH (As(V)) = 4.6
D = 1 g/L
Punica granatum L. Pb2+ 371.36 – pH = 5 0.999 Langmuir [135]
D = 0.5 g/dm3
Co = 145 mg dm3–300
mg/dm3
T = 20–50 ◦ C
Black gram husk Cr(VI) 333.33 – CT = 180 min 0.9427 Langmuir [136]
Banana stalk Pb2+ 13.53 96.76 pH = 9 0.99 Langmuir [31]
T = 318 K
Banana peel Fe2+ 0.93 – Co = 100–500 mg/L 0.93 Langmuir [137]
Banana stem Hg2+ 132.25 – T = 30 ◦ C 0.999 Freundlich [138]
pH = 7
D = 2 g/L
*
Unit: mmol/g.
efficiency [142]. Chemical modifications can change the biosorbent Table 5. After achieving the desired size, various types of modifying
behaviour in terms their ability to participate in ion exchange, their agents as mentioned in Fig. 2, including acids, bases, and organic
hydrophobicity/hydrophilicity, the elasticity and thermal resistance compounds are used for chemical pre-treatment. By treating the bio
[67]. Generally, prior to performing chemical modifications, the bio sorbent surface with acids and bases, the surface gets oxidized and forms
sorbent undergoes various steps such as washing, drying, crushing, functional groups that can overall enhance the sorption capacity [144].
grinding and sieving [95,127,143]. A list of such modifications con Other methods such as biosorbent immobilization which include cross
ducted on various agriculture waste based biosorbents are presented in linking of polymers are also used. Graft polymerization is another
9
Table 4
Adsorption kinetics for various agriculture waste-based adsorbents.
Biosorbent Metals removed Experimental conditions Removal R2 Adsorption kinetics Reference
2+
Coffee waste Pb pH = 7.3 10.0908 0.9998 Pseudo-second-order [87]
T = 25 ◦ C
2+
Orange eel Pb CT = 0–400 min 24.28 0.9997 Pseudo-second-order [88]
Cd2+ Co = 40 mg/L 21.53 0.9956
Ni2+ T = 30 ◦ C 20.82 0.9936
Orange peel Cd2+ Co = 20 mg/L 0.0060 1 Pseudo-second-order [89]
Cu2+ CT = 5–20 min 0.172 1
Pb2+ pH = 5 0.052 1
T = 25 ◦ C
Banana peel Cr(VI) D=1g 359.97 0.99 Pseudo-second-order [85]
Te = 60 min
Co = 1200 mg/L
Orange peel Pb2+ D = 500 mg 9 1 Pseudo-second-order [91]
Zn2+ Co (Pb2+) = 100 mg/L
Co (Zn2+) = 50 mg/L pH = 5.0
Litchi peels Pb2+ Co = 50 mg/L 9.46 0.9999 – [92]
D = 0.25 g
T = 25 ◦ C
pH = 6.0
Pineapple peel Cd2+ Te = 30 min 43.48 0.995 Pseudo-second-order [93]
Pb2+ D = 0.2 g 33.34 0.993
T = 25 ◦ C
pH: 4
Co = 100 mg/L
Lemon peel Ni2+ Co = 100 mg/L 20.006 0.991 Pseudo-first-order [94]
pH = 5
D = 5 g/L
Tomato waste Pb2+ D = 0.2 g 4.958 0.999 Pseudo-second-order [98]
T = 25 ◦ C
pH = 4
Co = 100 mg/L
Peanut husk Ni2+ CT = 0–200 min 0.123 0.996 Pseudo-second-order [100]
pH = 6.5
D = 22.5 g/L
Sugarcane bagasse As(III) CT = 5–120 min 0.0392 0.983 Pseudo-second-order [139]
D = 10 g/L
Co = 0.395 mg/L
Te = 90 min
Sugarcane bagasse Co2+ pH (Co2+) = 5.75 1.153 ± 0.035 0.9580 Pseudo-second-order [108]
Cu2+ pH (Cu2+) = 5.5 0.979 ± 0.051 0.8694
Ni2+ pH (Ni2+) = 5.75 0.849 ± 0.020* 0.9671
T = 25 ◦ C
D = 0.2 g/L
Co = 0.79 mmol/L
Rice husk Cd2+ T = 25 ◦ C 9.80 0.999 Pseudo-second-order [110]
Ni2+ pH = 4 10.20
Co = 60 mg/L
Rice husk Cd2+ Co = 10 to 250 mg/L 118.30 0.9999 Pseudo-second-order [70]
CT = 120 min
pH = 7
Cashew nut shell Cu2+ Co = 20–100 mg/L 10.869 0.997 Pseudo-second-order [111]
D = 0.2 g
pH = 6
T = 30 ◦ C
Cashew nut shell Pb2+ Co = 10 and 50 mg/L 2.26 0.9692 Pseudo-first-order [112]
Groundnut hull Cr(VI) pH = 2 5.435 0.9992 Pseudo-second-order [113]
Citrus lemon peels U(VI) T = 25.0 ± 0.5 ◦ C 16.13 0.999 Pseudo-second-order and Weber–Morris [114]
pH = 8.0
Garlic peel Pb2+ Co = 150 μg/mL 105.82 0.999 Pseudo-second-order [115]
pH = 5
CT = 40 min
Grapefruit peel Cr(VI) Co = 35 mg/L 1.8280 0.9996 Pseudo-first-order [117]
CT = 24 h
Cucumber peel Cd2+ Te = 60 min 0.265* 0.999 Pseudo-second-order [120]
pH = 5
T = 30 ◦ C
CT = 180 min
Lemon peel Co2+ D = 2 g/L 26.810 0.995 Pseudo-second-order [121]
Co = 100 mg/L
pH = 6,
T = 30 ◦ C
Mg-orange peel Pb2+ Co = 100 mg/L 20 1 Pseudo-second-order [91]
Zn2+
K-orange peel Cu2+ 9.41 1 Pseudo-second-order [123]
10
Biosorbent Metals removed Experimental conditions Removal R2 Adsorption kinetics Reference
Co = 50 mg/L
D = 5 g/L
T = 25 ◦ C
Te = 20 min
pH = 5.3
Orange peel Cu2+ Co = 50 mg/L 9.61 1 Pseudo-second-order [123]
D = 5 g/L
T = 25 ◦ C
Te = 20 min
pH = 5.3
Peanut hull Ni2+ pH = 6, 3.3967 0.9986 Pseudo-second-order [127]
T = 25 ◦ C
D = 5 g/L
CT = 30 min
Banana peel Pb2+ CT = 0–500 min 78.19 0.999 Pseudo-second-order [30]
Te = 300 min
Green tea waste As(III) D = 0.3 g 0.4212 0.9990 Pseudo-second-order [128]
pH = 3
T = 33 ◦ C
Green tea waste Ni2+ D = 0.3 g 0.3116 0.9989 Pseudo-second-order [128]
pH = 3
T = 33 ◦ C
Tea waste Pb2+ Co = 10 mg/L 22.2 0.989 Pseudo-first-order [131]
Cd2+ 18.8 0.992
Watermelon rind As(V) D = 1 g/L 3.56 ± 0.11 0.99 Pseudo-second-order [134]
As(III) Co As(III) and As(V) = 0.01–7 mg/L
T = 20 ◦ C
Punica granatum L. Pb2+ pH = 5.5 259.79 0.999 Pseudo-second-order [135]
Co = 145–200 mg/dm3
Black gram husk Cr(VI) – 256.4103 0.991 Pseudo-first-order [136]
Banana stalk (acid modified) Pb2+ T = 30 ◦ C 9.950 0.999 Pseudo-second-order [31]
Banana stalk (base modified) Pb2+ T = 30 ◦ C 2.749 1 Pseudo-second-order [31]
*
Unit: mmol/g.
method in which long polymer chains such as acrylic acid, acrylamide, behaviour make them favourable for adsorption processes.
acrylonitrile, hydroxylamine, and glycidyl monomers are introduced on The main mechanisms of sorption by magnetic biosorbents are ion
the biosorbent backbone to enhance biosorption. [57]. exchange, electrostatic interaction, precipitation, and complexation.
Magnetic biosorbents can contribute towards ion exchange through
5.1.1. Biosorbent composites their metal-based functional groups [158]. They can also contribute to
In synthesizing a biosorbent composite, generally two or more redox reactions due to their surface charge [65]. Most of the biosorbents
selected materials are combined together to create a composite with are diamagnetic in nature which is why they need to be modified by
improved properties [149]. Biosorbents can also be combined with other superparamagnetic, ferromagnetic and ferrimagnetic particles to
organic compounds or metal oxides to achieve better biosorbent prop become magnetically active. Superparamagnetic magnetic iron oxide
erties [144]. Some examples of composite materials that can be incor particles that are commonly used are magnetite (Fe3O4) and maghemite
porated in biosorbents are NaNO3, polyvinyl alcohol, polyvinyl chloride, (Fe2O3). Polysaccharide biopolymers such as cellulosic material are
dimethylamine, metal salts such as iron salt, copper salts, zinc salts, etc. commonly used for magnetic modification due to their ability to
[150–152]. Among composite materials, metal oxide salts have been of improve and tune the chemical affinity towards specific heavy metals in
great interest to researchers and has been explored extensively. This is wastewater. There are various methods to prepare magnetic biosorbents
because metal oxide salts can be used to produce magnetized particles such as co-precipitation, reactions in microemulsions, hydrothermal
which can then produce enhanced biosorbents with magnetic properties reactions, sol-gel syntheses, reactions, hydrolysis and thermolysis of
that can be separated and reused easily. The combination with metal precursors, mechanochemical processes and microwave synthesis. Co-
oxide salts can significantly enhance the biosorption capacity precipitation is more commonly used to prepare magnetic biosorbents
[153,154]. Magnetic biosorbents are generally prepared by treating the [159,160].
biosorbent material with metallic salts such as iron chloride hexahy
drate, iron sulphate heptahydrate, manganese oxide tetrahydrate and
manganese sulphate hydrate [155]. 5.2. Studies on chemical modification of biosorbents
When choosing a biosorbent for heavy metal removal, the ability of
the adsorbent to be separated from the adsorbate is one of the most In this section, various agricultural waste-based adsorbents have
crucial criteria. Otherwise, there will be secondary pollution which will been discussed, focusing on their chemical modification, adsorption
also increase the cost of the operation and maintenance. Magnetic bio mechanisms and functional groups involved in the uptake of heavy
sorbents can be easily separated under the influence of an external metals. Factors affecting biosorption such as contact time (CT), equi
magnetic field [24]. In adsorption processes, smaller sized magnetic librium contact time (Te), temperature (T), initial metal ion concentra
materials have advantages due to their high surface area-volume ratio. tion (Co), dosage (D) and pH are also discussed. The mechanisms and
Magnetic nanoparticles fall under the particle size of 100 nm and are functional groups involved in various adsorbents is listed in Table 6
single domain particles, exhibiting a superparamagnetic behaviour whereas the data on modifying agents and the adsorbents performance is
[156]. In the absence of an external magnetic field, these magnetic listed in Table 7.
nanoparticles have zero magnetization, no coercivity and are less likely
to agglomerate [157]. These consequences of the superparamagnetic 5.2.1. Chemical modification of biosorbents using metal and inorganic salts
It has been reported that biosorption efficiency can be enhanced by
11
Table 5 Table 5 (continued )

Brief overview of preparation of various agriculture based adsorbents. Biosorbent Metals Preparation Reference
Biosorbent Metals Preparation Reference removed
removed
Sundried → cutting → washing →
Orange peel Cd2+ Soaking → rinsing → drying in sun [89] oven drying → sieving → soaking in
Cu2+ → crushing → sieving H3PO4 and KOH each in the oven
Pb2+ Banana stem Hg2+ Crushed → dried → washed → oven [138]
Orange peel Pb2+ Washing → oven drying → crushing [91] drying → grounding → treating
Zn2þ → sieved → pre-treated NaOH + with each H2SO4 and HCHO →
ethanol → decantation → filtration stirring → washing → drying →
→ washing → oven drying → sieving
stirring in mercapto-acetic acid → Rice husk Fe2+ Washing → sun drying → oven [146]
decantation → filtration → washing drying → powdering → sieving →
→ oven drying → crushing mixing with NaOH → washing →
Orange peel Cu2+ Cutting → drying → washing → [32] drying
Pb2+ oven drying → crushed → sieved → Date palm fruit Cr(VI) Washing → grinding → shredding [147]
Zn2+ soaking in sodium hydroxide and empty fruit → drying → powdering → sieving
calcium chloride and ethanol bunch
solutions → decantation → Tea waste Pb2+ Washing → self-desiccation → [148]
filtration → washing → drying drying → grinding → sieving →
Pineapple peel Cd2+
Washing → drying → grinding → [93] mixing with H2SO4 → washed →
Pb2+ sieving → treating and stirring with filtered → oven drying
H2SO4 and 100 mL of 0.1 M KMnO4
solution → washing oven drying
Lemon peel Ni2+ Washed → oven drying → ground in [94] using metal salts and inorganic salts. Moreover, metal and inorganic
coffee mill → sieving → stirring salts do not cause a mass loss in the biosorbents like acids or bases do. In
with HNO3 → HCl → H3PO4 → NH3
a study conducted by Guo et al. [33], the authors modified orange peels
→ CaCl2 → & NaOH → washing →
oven drying with KCl to study the removal of Cu2+, Cd2+, Pb2+, Zn2+ and Ni2+ from
Papaya peel Cu2+ Washing → drying → soaking in [145] aqueous solution. Orange peels constitutes of cellulose, hemicellulose
NaOH → stirring → oven drying → and lignin which form carboxyl and hydroxyl functional groups that are
grounding in blender sieving efficient in heavy metal uptake [124]. Modification using KCl can be
Tomato waste Pb2+ Stirring of NaOH + biosorbent → [98]
filtered → washed → oven drying →
used to initiate an ion exchange reaction between H+ of carboxylic acid
sieving present on the orange peel surface and the Na+, Mg2+ or K+ ions to
Peanut husk Ni2+ Washing → oven drying → milled in [100] increase ion-exchange capability [123]. In this study, adsorption equi
coffee mill → oven drying → stored librium was attained after 20 min. The adsorption followed a pseudo-
in desiccator → soaking in NaOH
second-order kinetics indicating that the adsorption took place
and HNO3 solution → washing →
oven drying through chemisorption. The study also included adsorption experiments
Sugarcane As(III) Mixing and stirring with [106] in a single and binary metal system to study the effects of competing
bagasse As(V) mercaptoethanol → washing → ions. The results showed that adsorption was equally efficient in both
oven drying the systems. It has been reported that ZnCl2 can improve mesopores,
Citrus lemon U(VI) Cutting → washing → air drying → [114]
peels stirring with HNO3 → rinsing → air
specific surface area and micropores of a biosorbent [59,158]. Pei and
drying → Soaking in NaOH → Liu [118] modified grapefruit peel by using ZnCl2 as an activating agent
washing → air drying → blending for the removal of lead ions from aqueous solution. Upon investigation,
→ sieving the authors concluded that the sorption occurred through chemisorp
Musk melon peel Pb2+ Cutting → mixing with calcium [116]
tion. Ion exchange between lead ions and biosorbent surface had taken
hydroxide and deionized water →
stirring → filtering → washing → place. Introduction of negatively charged Cl− groups could also partic
oven drying → meshing ipate in metal binding. The biosorbent surface consists of oxygen rich
Lemon peel Co2+ Washing → crushing → washing → [121] functional groups which will interact with the lead ions and undergo
oven drying → sieving → agitation chemical adsorption. After that, the lead ions will accumulate on the
with each NaOH → HCl → H2SO4 →
HNO3 and H2O2 → washed → oven
surface of the biosorbent by means of physical adsorption. From these
dried case studies, it is evident that when a metal or organic salt is used for
Orange peel Cu2+ Washed → oven dried → crushed → [123] modifying a biosorbent, it promotes an ion exchange reaction between
sieved → soaking in ethanol and the heavy metal and the modified biosorbent surface. Similarly, in a
NaOH → stirring → adding each of
study conducted by Mohamed et al., [169], the authors modified banana
MgCl2 or KCl → filtration →
washing → oven drying → crushing peel with KOH for the removal of Pb2+ and Fe2+ ions. The results
→ sieving demonstrated that the maximum removal efficiency reached 100% and
Tea waste Pb2+ Cleaning → washing → rinsing → [131] 64%, respectively. It was reported that the addition of KOH to the un
Cd2+ powdering → sieving → drying in treated banana peel hydrolysed the peel and promoted the formation of
furnace. For nanoparticles →
absolute ethanol-water sonication
hydroxyl and carboxyl groups. Increasing the amount of KOH created
→ adding tetraethoxysilane to the stronger and broader peaks when analysed. Therefore, treating the
mixture → sonication → samples with KOH increased the oxygen containing functional groups.
centrifugation → washing → oven The main adsorption mechanisms were expected to be ion exchange and
drying. For tea waste@SiO2 → Tea
surface complexation with carboxyl and hydroxyl groups.
leaves + Millipore water → silica
nanopowder + tea leaf solution
stirring → sonicating → centrifuged 5.2.2. Chemical modification of biosorbents using bases
→ dried It has been reported that alkali treatment of biosorbents can increase
Banana stalk Pb2+ [31] the porosity of a biosorbent and incorporate new functional groups
which can participate in biosorption through mechanisms such as ion-
exchange [144]. Calcium hydroxide is commonly used saponifying
12
Fig. 2. Some examples of modifying agents used in chemically modifying biosorbents.
agent used to modify biosorbents to improve the uptake of heavy metals very quickly, within 10 min. The adsorption capacity increased after
[128]. It has been reported that calcium hydroxide causes a crosslinking modification from 44.28 mg/g to 70.73 mg/g for Cu2+, 113.5 mg/g to
reaction with the molecules of the biosorbent [187]. In a study con 208.9 mg/g for Pb2+ and 21.25 mg/g to 56.18 mg/g for Zn2+. The
ducted by Peng et al. [124], orange peel modified with Ca(OH)2 was modified adsorbent also showed high selectivity towards Pb2+ and Zn2+.
used to study the removal arsenic from aqueous solution. In this study, The adsorption capacities (metals adsorbed per gram of biosorbent) as
the surface morphology was analysed through SEM analysis. The SEM achieved by the biosorbents were analysed in terms of the Ca2+ ions
images after chemical modification depicted a heterogeneous surface remaining inside the aqueous solution. It was evident that ion exchange
which was favourable for arsenic adsorption. It was reported that As(V) process took place between the cationic metal ions and Ca2+. The
exists mainly as H2AsO4− between a pH range of 3 and 6. Therefore, in mechanism of adsorption can be described as ion exchange between the
this study, adsorption could have taken place due to the substitution of heavy metal ions and calcium ions chelated to the carboxylic groups on
COOH/OH groups with the ions of H2AsO4− present on the surface of the the polymeric structure of pectin in the adsorbent. Additionally, modi
biosorbent [188]. Furthermore, the FTIR spectra confirmed the presence fying a biosorbent with a base can increase the negative charge on the
of metal binding functional groups such as carboxylic groups and hy surface of the biosorbent and increase the electrostatic interactions be
droxyl group (N–H, –OH band at 3427.93 cm− 1, 1649.61 cm− 1 and tween the negatively charged biosorbent surface and the cationic heavy
1033.23 cm− 1, C–N band at 1242.20 cm− 1, C– – O band at C–H band at metals ions. Similarly, Ayob et al. [179] also modified pineapple waste
2927.44 cm− 1) that would participate in ionization and the removal of using NaOH for the removal of lead form aqueous solution. The
arsenic. Similarly, muskmelon peel was modified with Ca(OH)2 and used adsorption efficiency increased from 52.57% to 85.88% after modifi
as a biosorbent for the removal of Pb2+ by Huang and Zhu [116]. cation. This was because after treating the pineapple waste with NaOH,
Muskmelon peel consists of protein, cellulose and polysaccharides such the adsorbent is expected to undergo deprotonation. The Na ions in the
as pectic acid. These functional groups are associated with metal binding NaOH are more electropositive than Pb2+ which allows a displacement
functional groups such as –COOH and –OH. About 10% of the musk reaction between the sodium and lead ions. Additionally, ion exchange
melon peel consists of pectic acid (dry weight). Pectic acid is also the between the lead ions and the carboxylate and hydroxyl anionic groups
source of functional ligands which can participate in the uptake of lead present on the adsorbent surface can occur.
ions. After modification with Ca(OH)2, the pectic acid will be converted
to pectic calcium and participate in forming bonds with the positively 5.2.3. Chemical modification of biosorbents with acids
charged lead ions. Cationic exchange between the Ca2+ and Pb2+ is the Modification of biosorbents with acids helps to remove impurities
main biosorption mechanism in this study. Similar cation exchange and unwanted compounds from the biosorbents surface. There have
mechanism was reported by Feng and Guo [32], when the authors used been various studies in which the biosorption efficiency was improved
sodium hydroxide and calcium chloride to modify orange peel for the by using acids as modifying agents. According to Horsfall et al. [189],
removal of Cu2+, Pb2+and Zn2+. SEM analysis conducted in this study mercaptoacetic acid causes thiolation (incorporation of sulfhydryl
revealed that after modification with sodium hydroxide and calcium groups) of the –OH functional groups that are abundantly available on
chloride, the biosorbent surface showed more irregularities and pores. cellulose backbone. There have been various studies in which re
The surface area was analysed by BET method and the results showed searchers have modified agricultural wastes using mercaptoacetic acid.
that modified orange peel had a surface area of 1.496 m2/g and the In a study conducted by Liang et al. [91], the authors used orange peels
unmodified orange peel had a surface area of 0.828 m2/g denoting that modified with mercaptoacetic acid for the removal of Pb2+and Zn2+
the surface area had increased after chemical modification. Increase in from aqueous solution. FTIR analysis confirmed that hydroxyl, carboxyl
surface area means that there will be more active sites available for and mercapto groups were responsible for the adsorption. The modified
heavy metal adsorption. The metal uptake process reached equilibrium orange peel can adsorb heavy metal ions through cation exchange,
13
Table 6
Mechanisms and functional groups involved in the adsorption of heavy metals using various agricultural waste based adsorbents.
Biosorbent Metals Maximum % Mechanism/remarks Functional groups (FG)/remarks (R) Reference
removed removal (mg/ Removal
g)
Coffee waste Pb2þ 41.15 – Ion exchange FG: Hydroxyl groups [87]
Orange peel Pb2þ 476.1 – Ion exchange, Chelation FG: Carboxyl and hydroxyl group [88]
Cd2þ 293.3
Ni2+ 162.6
Orange peel Cd2þ 13.7 – Ion exchange FG: Carboxylate group [89]
Cu2þ 15.27
Pb2+ 73.53
Orange peel Pb2þ 164 – Ion exchange/complexation FG: Sulfhydryl group, hydroxyl group and carboxyl group [91]
Zn2þ 80
Orange peel Cu2þ 70.73 – Ion exchange R: The biosorption was mainly due to ion exchange [32]
Pb2þ 209.8 between calcium ions and cations. X- ray fluorescence
Zn2+ 56.18 analysis showed that the calcium
and copper concentrations were approximately 7.271%
and 0.007% before the adsorption and 1.908% and
11.610% after the copper adsorption
Litchi peels Pb2+ 78.74 – Chemisorption FG: Hydroxyl, amido, and carbonyl groups were [92]
Pineapple peel Cd2þ 42.10 – Electrostatic attraction/chelation FG: Carboxyl groups, hydroxyl groups, amino groups [93]
Pb2+ 28.55 between
Lemon peel Ni2+ 36.74 – Electrostatic interaction FG: Carboxyl groups, hydroxyl functions, alkyl groups [94]
Papaya peel Cu2+ – 79 Complexation FG: Carboxyl and hydroxyl group [145]
Banana peel Cd2þ 27.77 – Complexation FG: Carboxyl and hydroxyl group [97]
Cr3þ 38.46 R: Banana peels are rich in polysaccharides, which are
Zn2+ 9.52 mainly cellulose and pectin compounds as galacturonic
acid polymers. These compounds consist of oxygen rich
such as -OH groups which promote adsorption
Kiwi cortex Cd2þ 15.87 – Complexation FG: Carboxyl and hydroxyl group [97]
Cr3þ 41.66 R: Abundant in pectin and cellulose
Zn2+ 37.03
Tangerine Cd2þ 17.54 – Complexation FG: Carboxyl and hydroxyl group [97]
Cr3þ 47.61
Zn2+ 38.41
Tomato waste Pb2+ 152 – Chemisorption FG: Hydroxyl group [98]
Pomelo peel Cu2+ 8 – Ion exchange FG: Hydroxyl group [161]
Peanut husk Ni2+ 0.1473 – Chemisorption – [100]
Peanut husk Cr(VI) 33.11 – Electrostatic attraction FG: Amino groups, carbonyl groups [101]
Sugarcane bagasse Cd2þ 33.2 – Complexation, electrostatic FG: Hydroxyl and carboxyl groups, carbonyl groups [102]
Pb2+ 116.7 attraction, cation-π interaction
and physisorption
Sugarcane bagasse As(III) – 98.9 Surface adsorption and intra- – [139]
particle pore diffusion
Wheat straw Pb2+ 50.76 – Chemisorption FG: Hydroxyl and carboxyl groups [35]
Sugarcane bagasse As(III) 28.57 – Complexation, electrostatic FG: Thiol groups [106]
As(V) 34.48 interaction
Sugarcane bagasse As(V) 22.1 – Surface precipitation, ion FG: Carboxyl and hydroxyl groups [107]
exchange and complexation
Citrus lemon peels U(VI) 24.39 – Chemisorption, ion exchange, FG: Carboxyl and hydroxyl groups [114]
complexation
Garlic peel Pb2+ 109.05 – Ion exchange FG: Carboxyl and hydroxyl groups [115]
Musk melon peel Pb2+ 167.8 – Ion exchange FG: –COOH and –OH [116]
R: Pectic acid in the peel also played a major role in
adsorption of lead ions
Grapefruit peel Cr(VI) 39.0628 – Chemisorption FG: Carboxylic groups, phenolic and laconic groups [117]
Grapefruit peel Pb2+ 12.73 – Ion exchange, physisorption FG: Oxygen containing functional groups such as OH [118]
Lemon peel Co2+ 59.77 – Ion exchange FG: Carboxyl groups, hydroxyl group [121]
Orange peel Pb2þ 7.44 – Ion exchange, or complexation FG: hydroxyl group, mercapto groups [91]
Zn2+
Orange peel Cr(VI) 40.37 – Redox reactions, Van der Waals FG: Hydroxyl groups [122]
forces, electrostatic forces and R: Iron ions and hydroxyl groups undergo redox reaction
hydrogen bonds
Orange Cu2+ 59.77 – Chemisorption, ion exchange FG: Hydroxyl and carboxylic acid groups [123]
peel‑magnesium
modified
Orange Cu2+ 43.69 – Ion exchange FG: Hydroxyl and carboxylic acid groups [123]
peel‑potassium
modified
Peanut hull Ni2+ 90 – Electrostatic interaction FG: O–H, C–H, C–O and Fe–O [127]
Green tea waste As(III) 0.3116 – Ion exchange, hydrogen bonding FG: –COOH and –OH [128]
Green tea waste Ni2+ 24.39 – Ion exchange FG: –COOH and –OH [128]
Tea waste Pb2þ 38.3 – Surface charge, formation of FG: Si–O, OH–, COO− [131]
Cd2+ covalent bonds, cation interaction
and ion exchange
Tea waste Ni2+ 2.230 – FG: Carboxyl and hydroxyl groups [132]
14
Biosorbent Metals Maximum % Mechanism/remarks Functional groups (FG)/remarks (R) Reference
removed removal (mg/ Removal
g)
Ion exchange, electrostatic

interaction
Watermelon rind As(V) 75.76 98 Ion exchange, chemisorption FG: –OH, –COOH, S–bearing, C–
–S, S–
–O and S–S groups [134]
As(III) 63.93 99
Acid activated Pb2+ 13.53 96.13 Chemisorption FG: Carboxyl, hydroxyl and phenolic [31]
Banana stalk
Base activated Pb2+ – 66.90 Chemisorption FG: Carboxyl, hydroxyl and phenolic [31]
Banana stalk
Banana stem Hg2+ 5.3 – Ion exchange FG: –SO3H, C––O [138]
Rice husk Fe2+ 5.6 – Ion exchange, chemisorption, FG: Ester, phenol, carbonyl and siloxane groups [146]
electron sharing
Date palm fruit Cr(VI) 70.49 58.02% Electrostatic attraction, following FG: Hydroxyl, amines, esters, carboxylic acids, alcohols [147]
empty fruit bunch a surface protonation of these and ethers
sites, surface complexation
Tea waste Pb2+ – 97.73% Complexation, coordination FG: Carbonyl and carboxyl group [148]
bonding, electron pairing
complexation or even through a combination of both the processes. In carboxylic acid sites that have contributed to increasing the adsorption
the reaction mechanism, functional groups such as –OH, –SH and capacity [192]. Citric acid modification has been reported to increase
–COOH will release H+ ions into the aqueous solution and the heavy cationic exchange properties of the biosorbent [193]. In a study con
metal ions will be adsorbed on the active sites of the biosorbent. The ducted by Liu et al. [102], the authors modified sugarcane bagasse with
authors noticed a significant improvement from 90 mg/g to 164 mg/g citric acid and Fe3O4 for the removal of Cd2+and Pb2+ from aqueous
for Pb2+ and 25 to 80 mg/g for Zn2+ after modification with mercap solution. Citric acid is known to be a chelator that can combine itself
toacetic acid. Ion exchange is a predominant biosorption mechanism with heavy metal ions such as Cd, Cu and Pb to limit their mobilization.
that takes place between heavy metal ions and functional groups. For Also, esterification between hydroxyl groups and citric acid can produce
example, Lasheen et al. [89] used acid treatment to modify orange peel more functional groups and active sites on the surface of the biosorbent.
by protonation with HNO3 to study the removal of Cd2+, Cu2+, and Pb2+ The sugarcane bagasse showed higher removal capacity after chemical
from aqueous solution. Soaking the orange peel in HNO3 followed by modification. The biosorption was found to be mainly due to the oxygen
rinsing and drying unnecessary components that would block the active containing functional groups such as carboxylic and hydroxyl groups.
sites, thereby exposing them for adsorption to take place. Protonation of FTIR analysis indicated the occurrence of complexation with the
the biosorbent also reduces the competition between ions such as Ca2+ carbonyl groups. It also revealed that a number of carboxylic groups also
and K+ so that metal ions can bind the available active sites. The FTIR participated in the adsorption by sharing oxygen electrons with the Cd2+
spectra analysis revealed a change in bonding pattern of the carboxylate and Pb2+ ions. Similar analysis has been reported by Vaughan et al.
group present in pectin which indicates its involvement in the bio [192]. It was reported that in an esterification reaction, when a citric
sorption process. Similar results were observed by Fu and Wang [15]. acid molecule is attached to the cellulose of a corncob, each citric acid
Suyono et al. [96] also used HNO3 to modify petai peels and papaya molecule attached produced an additional two carboxylic acid groups
leaves for the removal of Pb2+ ions from aqueous solution. FTIR analysis for biosorption and thereby increased the adsorption capacity. It was
revealed that the dominant functional groups participating in adsorp reported by Özer et al. [194] that chemical treatment with acids such as
tion present on petai peels and papaya leaves were the hydroxyl and H2SO4 can convert macropores into micropores. This can cause a change
carboxyl groups. Nitric acid also has the ability to increase the acidic in the surface area. H2SO4 also removed potassium and chlorine from
groups on the surface of the biosorbent by reacting with the functional the surface of the biosorbent. After removing these groups, carbon, ox
groups that are basic in nature to produce more acidic functional groups ygen and sulphur groups were left on the surface. These groups are ex
through heterocyclic opening [190]. Petai peel followed Langmuir pected to engage in biosorption. Similarly, Martín-Lara et al. [105] also
isotherm indicating a homogenous monolayer adsorption whereas used H2SO4 to modify sugarcane bagasse for the removal of lead ions
papaya peels followed Freundlich isotherm indicating multilayer from aqueous solution. Chemical modification with H2SO4 produced
adsorption. Before adsorption, SEM analysis showed a porous biosorbent more negatively charged functional groups such as carboxylic acid. The
surface. After adsorption took place, these pores were smaller which treatment is also expected to cause an increase in the surface area and
indicates the accumulation of the heavy metals ions in the pores. In oxidize the functional groups present on the biosorbent to carboxylic
another study conducted by Burevska et al. [100], HNO3 was used to groups which will enhance biosorption. Carboxylic acid is expected to
modify peanut husks for the removal of Ni2+ ions. SEM analysis of the increase the biosorption of lead ions. Amine groups were also found at a
peanut husk before chemical modification depicted a rough surface with pH of 10 and could have contributed towards the biosorption. The
numerous pores and cavities. After chemical modification, new cavities adsorption capacity before and after biosorption increased from 6.366
and pores were spotted. This improved the structure of the biosorbent mg/g to 7.297 mg/g. In a study conducted by Ahmad et al. [195],
and contributed to the increase in the specific surface area and increased pineapple fruit peel was modified by oxidizing it with H2SO4 and KMnO4
the biosorption capacity. The adsorption isotherm studies revealed that to study the removal of Cd2+ and Pb2+ from aqueous solution. The au
peanut husks modified with HNO3 showed better adsorption capacity thors reported that the chemical modification greatly enhanced the
when compared to natural peanut husk. As reported by Nguyen et al. biosorption capacity. The biosorption capacity for both the metal ions
[191], oxygen and nitrogen content increases with nitric acid treatment was higher for the modified pineapple peel. It was hypothesized that
whereas carbon content reduces. This could be due to (1) more number biosorption may have taken place through chelation/electrostatic
oxygen-containing functional groups involving phenolic, carboxylic and attraction between the anionic ligands i.e. COO− , OH− and the metal
nitro moieties on the surface and (2) due to more number of NO3 and ions while the carboxyl/hydroxyl groups undergoes deprotonation at a
NO2 groups resulting from nitric acid. Therefore, oxidation via nitric pH range of 3–4. Moreover, adsorption isotherm studies revealed that
acid could increase the biosorption ability of a biosorbent. the data fit best with the Langmuir isotherm which implies that the
In various studies, biosorbents modified by citric acid have produced process was a homogenous and monolayer adsorption. The biosorption
15
Table 7
The performance of chemically modified agricultural waste materials in removing heavy metals from water.
Biosorbent Metals removed Maximum removal (mg/g) % Removal Modifying agent/pre-treatment Reference
2þ
Coffee waste Pb 41.15 – Fe3O4 nanoparticles [87]
Orange peel Pb2þ 476.1 – Methyl acrylate [88]
Cd2þ 293.3
Ni2+ 162.6
Orange peel Cd2þ 13.7 – HNO3 [89]
Cu2þ 15.27
Pb2+ 73.53
Banana peel Cr(VI) 6.1728 96 Acrylonitrile [85]
Banana peel Mn2+ 5.7306 94 Acrylonitrile [90]
Orange peel Pb2þ 164 – Mercapto-acetic acid [91]
Zn2þ 80
Orange peel Cu2þ 70.73 – Sodium hydroxide and Calcium chloride [32]
Pb2þ 209.8
Zn2+ 56.18
Litchi peels Pb2+ 78.74 – Fe3O4 magnetic nanoparticles [92]
Pineapple peel Cd2þ 42.10 – Sulphuric acid and potassium permanganate [93]
Pb2+ 28.55
Lemon peel Ni2+ 36.74 – HNO3, HCl, H3PO4, CaCl2, NH3, NaOH [94]
Banana peel Pb2þ 89.286 – Sodium hydroxide [95]
Cu2+ 5.720
Lemon peel Cd2+ – 93.3 Al2O3 nanoparticles [34]
Lemon peel Ni2+ – 90±0.1 TiO2 nanoparticles [162]
Papaya leaves Pb2þ 284.35 – HNO3 [96]
Petai peel Pb2+ 36.01 – HNO3 [96]
Papaya peel Cu2+ – 79 NaOH [145]
Banana peel Cd2þ 27.77 – NaOH [97]
Cr3þ 38.46
Zn2+ 9.52
Kiwi Cd2þ 15.87 – NaOH [97]
Cr3þ 41.66
Zn2+ 37.03
Tangerine Cd2þ 17.54 – NaOH [97]
Cr3þ 47.61
Zn2+ 38.41
Tomato waste Pb2+ 152 – NaOH [98]
Pomelo peel Cu2+ 8 – Iron nanoparticles [161]
Pomelo peel Pb2+ – >95% Zinc chloride [163]
Peanut husk Cd2þ 7.68 – Magnetic iron oxide nanoparticles [99]
Pb2+ 28.3
Peanut husk Ni2+ 0.1473 – HNO3 [100]
Peanut husk Cr(VI) – – Formaldehyde [101]
Peanut husk Cr(VI) 33.11 – Formaldehyde and Fe [101]
Sugarcane bagasse Cd2þ 33.2 – Citric acid and Fe3O4 [102]
Pb2+ 116.7
Sugarcane bagasse As(III) – 98.9 Iron oxide [139]
Sugarcane bagasse Zn2þ – 74.91 EDTA [103]
Cr(VI) 76.54
Sugarcane bagasse Pb2+ 52.63 – Citric acid [104]
Sugarcane bagasse Pb2+ 30.68 – Sodium hydroxide [104]
Sugarcane bagasse Pb2+ 35.09 – Citric acid and sodium hydroxide [104]
Sugarcane bagasse Pb2+ 7.297 – Sulphuric acid [105]
Sugarcane bagasse Cd2þ 2.137 – Sodium hydroxide [29]
Cr2þ 6.782
Pb2+ 21.242
Sugarcane bagasse Cd2þ 1.917 – Nitric acid [29]
Cr2þ 5.393
Pb2+ 18.724
Sugarcane bagasse Cd2þ 2.221 – Sulfuric acid [29]
Cr2þ 5.122
Pb2+ 23.251
Wheat straw Cd2þ 3.075 – Sodium hydroxide [29]
Cr2þ 7.550
Pb2+ 21.237
Wheat straw Cd2þ 3.883 – Nitric acid [29]
Cr2þ 6.677
Pb2+ 22.398
Wheat straw Cd2þ 2.776 – Sulphuric acid [29]
Cr2þ 6.081
Pb2+ 18.345
Wheat straw Pb2+ 50.76 – Iron nanoparticles [35]
Sugarcane bagasse As(III) 28.57 – 2-mercaptoethanol [106]
As(V) 34.48
Sugarcane bagasse As(V) 22.1 – Hydrated ferric oxide [107]
Sugarcane bagasse – Phthalic anhydride [108]
16
Co2þ 0.561*0.
Cu2þ 9350.
Ni2+ 932
Rice husk Ni2+ 26.6 63.57 NaOH [109]
Rice husk Cd2þ 45.5 – Tartaric acid [110]
Ni2+ 55.5
Rice husk Cd2+ 137.16 – Magnesium xanthate [70]
Cashew nut shell Cu2+ 48.05 – Nano zero-valent iron [111]
Cashew nut shell Pb2+ 8.30 – H2SO4 [112]
Cashew nut shell Pb2+ 6.39 – HNO3 [112]
Cashew nut shell Pb2+ 3.22 – NaOH [112]
Groundnut hull Cr(VI) 131 – Pyromellitic dianhydride [113]
Citrus lemon peels U(VI) 24.39 – Nitric acid, sodium hydroxide [114]
Citrus limetta peels Cd2+ 287.6 – Sulphuric acid [164]
Garlic peel Cd2+ 68.6 – Sodium hydroxide [165]
Garlic peel Pb2+ 109.05 – Sodium hydroxide [115]
Musk melon peel Pb2+ 167.8 – Calcium hydroxide [116]
Grapefruit peel Cr(VI) 39.0628 – Hydrogen peroxide [117]
Grapefruit peel Pb2+ 12.73 – Zinc chloride [118]
Grapefruit peel Cd2+ 42.09 – Methanol, hydrochloric acid, HCHO [119]
Ni2+ 46.13
Cucumber peel Cd2+ 0.998* – Methanol [120]
Lemon peel Co2+ 35.71 – Sodium hydroxide [121]
Orange peel Cu2þ 59.77 – Potassium chloride [33]
Orange peel Cd2+ 125.63 – Potassium chloride [33]
Orange peel Pb2+ 141.84 – Potassium chloride [33]
Orange peel Zn2+ 45.29 – Potassium chloride [33]
Orange peel Ni2+ 49.14 – Potassium chloride [33]
Orange peel Cr(VI) 7.44 – Iron oxide nanorods [122]
Orange peel Cu2+ 40.37 – Magnesium chloride [123]
Orange peel Cu2+ 59.77 – Potassium chloride [123]
Orange peel As(V) 43.69 95 Calcium hydroxide [124]
Cassava peel Hg2+ – 72.98 Citric acid [125]
Lemon peel Hg2+ – 49.83 Citric acid [125]
Corncob Pb2+ 0.2095* – Methanol [126]
Sodium hydroxide
Coconut fiber Cr(VI) 87.38 <90% Magnetite nanoparticles [143]
Peanut hull Ni2+ 8.63 – Magnetic iron nanoparticles [127]
Banana peel Pb2+ 90 – NaOH [30]
Green tea waste As(III) 0.4212 – Calcium hydroxide [128]
Green tea waste Ni2+ 0.3116 – Calcium hydroxide [128]
Coconut pith Ni2+ 24.39 – Sulphuric acid [129]
Tea waste U(VI) 111.61 – Graphene oxide [130]
Tea waste U(VI) 104.95 – Graphene oxide/magnetic Iron oxide [130]
Tea waste Pb2þ 153 – Silicon dioxide [131]
Cd2+ 222
Tea waste Ni2+ 38.3 – Magnetic nanoparticles (Fe3O4) [132]
Corn cob + petai hull Pb2+ 2.230 – Nitric acid [133]
Watermelon rind As(V) – 98 Carbon disulphide [134]
As(III) – 99
Corn cob Cu2+ 75.76 89.2 FeCl3⋅7H2O [166]
Zn2+ 63.93 89.3
Punica granatum L. Pb2+ 371.36 – Hexamethylenediamine [135]
Black gram husk Cr(VI) 215.27 – Fe3O4 nanoparticles [136]
Acid modified banana stalk Pb2+ 13.53 96.76 H3PO4 [31]
Based modified banana stalk Pb2+ – – KOH [31]
Banana peel Fe2+ 0.93 – Acrylonitrile [137]
Banana stem Hg2+ 132.25 – Formaldehyde [138]
Rice straw Cr(VI) 140.39 – Polyvinyl alcohol [167]
Pineapple leaf Cr(VI) 133 – Alkali solution [168]
Pineapple leaf Cr(VI) 222 – Polyethyleneimine [168]
Banana peel Pb2+ 0.9595 100 KOH [169]
Fe2+ 1.0505 64
Cassia fistula seeds Pb(II) 28.28 – HCl [170]
C. fistula seeds Pb(II) 129.3 – H2SO4 [170]
Jatobá-do-cerrado shell Cu(II) 33.96 – HNO3 and NaOH [171]
Ni(II) 41
Sugarcane bagasse Cr(VI) 156–251 – Polypyrrole [172]
Sugarcane bagasse Pb2+ 122.4 – Citric acid (pre-treated with ethanol) [173]
Sugarcane bagasse Pb2+ 97 – Citric acid (pre-treated with 0.01 M NaOH) [173]
Rice straw Cr(VI) 15.82 – Amine-functionalization [174]
Ni(II) 3.95
Modified cocoa shell Cr(VI) – 91–99 3-Aminopropyltriethoxysilane (APTES) [175]
Rubber leaf Cu(II) 9.074 – NaOH [176]
Sugarcane bagasse Cu(II) – 98.75 HCl [177]
Sugarcane bagasse Cu(II) 2.61 ± 0.01 – Fe3O4 nanoparticles [178]
17
Pineapple Waste Pb2+ – 85.88 NaOH [179]

Rice husk Arsenic 82 – Iron oxide [180]
Maize straw Cd(II) 196.1 – Succinic anhydride in xylene [181]
Rice husk Cu(II) 48.841 – NaOH [182]
Pomelo peel Cr(VI) 21.55 – FeCl3 [183]
Rice straw Cr(VI) 17.82 – Acrylamide (AM) and citric acid (CA) [184]
Maize husk Pb(II) 40.65 82.84 NaOH [185]
Tea waste Cr(VI) 158.73 – NaOH [186]
*
Unit: mmol/g.
of Cd2+ was seen to be significantly higher than Pb2+. This was attrib removal of Ni2+from aqueous solution. The effect of each modifying
uted to Pb2+ having a larger atomic radii of 1.20 Å in comparison to agent was studied. Surface treatment with NaOH showed the best re
Cd2+ that has an atomic radii of 0.97 Å which causes steric hindrance. In sults. It has been previously reported that chemical modification using
another study conducted by Hemavathy et al., [170], the authors alkaline treatments such as NaOH treatment increases the number of
modified Cassia fistula seeds with HCl and H2SO4 to remove lead ions carboxylate ligands for the metal-binding sites, allowing enhanced
from aqueous solution. Cassia fistula seeds modified with H2SO4 showed adsorption [198]. Villen-Guzman et al. [94] reported that the bio
the highest adsorption capacity. It was reported that the presence of sorption of nickel ions reached 100% with an adsorbent dose of 5 g/L.
alcohol, sulphates and phosphates on the surface of the adsorbent could The pectin, cellulose and pigments present in lemon peel consists of
promote hydrogen bonding with the lead ions. The lead ions were various functional groups such as carboxyl group, hydroxyl group and
adsorbed through hydrogen bonding and van der Waals forces between alkyl groups. FTIR analysis confirmed that after nickel ions were
the lead ions and the adsorbent surface. adsorbed on the lemon peel, there was a reduction in the peak intensities
of the C– – O and C–O due to the adsorption. Moreover, the peak in
5.2.4. Chemical modification of biosorbents by graft polymerization tensities associated with alkyl groups were reduced, indicating the
Another method of chemical modification is graft polymerization. In involvement of these groups in the biosorption process. These functional
this process, a side chains made up of monomers are covalently bonded groups promote metal binding. As depicted in Fig. 3, SEM micrographs
and polymerized on the cellulosic backbone, forming a copolymer. This showed that after modification with NaOH, even though there was some
process can improve the metal binding capacity of a biosorbent. For alteration in the surface structure, the superficial structure was main
example, in a study conducted by Ali et al. [85], it was reported that by tained. The change in surface irregularities could have contributed to
grafting acrylonitrile side chain onto the cellulosic skeleton of banana the improved adsorption of nickel ions. It was explained that the in
peels there was a significant improvement in the uptake of Cr (VI) from crease in adsorption capacity of the NaOH treated adsorbent was due to
ions from aqueous solution due to the enhancement in the metal- the conversion of the lignin structure into a negatively charged surface
biosorbent interaction. SEM analysis revealed that the unmodified ba which will strongly attract positively charged heavy metal ions. NaOH
nana peels had lignin, pectin and other viscous components. The modification may have also caused the metal hydroxides to micro-
modified banana peel depicted that the viscous components were precipitate, thereby increasing adsorption.
removed thereby revealing more pores and an uneven surface. After In another study conducted by Mahmood-ul-Hassan et al. [199], the
adsorption, the surface looked smoother due to the filling up of pores authors reported that chemical modification of banana stalks, corn cob,
with heavy metals. The adsorption followed the Langmuir isotherm and sunflower achene with NaOH gave the best adsorption results when
model which indicates that the uptake process is a monolayer adsorp compared to modifications using nitric acid and sulfuric acid for the
tion. Thermodynamic studies revealed that the process is exothermic, removal of Cd2+, Cr2+and Pb2+. The chemical treatment is expected to
feasible and spontaneous. Similarly, in another study conducted by Feng have facilated the hydrolysis of the hemicellulose with the acid/alkali.
et al. [88], the authors chemically modified orange peel by hydrolysing Chen et al. [200] explained that during hydrolysis, monomeric sugars
the grafted copolymer which was synthesised by interacting methyl and soluble oligomers are released from the cell wall matrix into the
acrylate with cross-linking orange peel to remove Pb2+, Cd2+, Ni2+ ions hydrolysate, thereby increasing the porosity and the heavy metal sorp
from aqueous solution. The maximum adsorption capacities by modified tion capacity. Low et al. [201] and Mahmood-ul-Hassan et al. [199] also
orange peel for Pb2+, Cd2+ and Ni2+ ions were 476.1, 293.3 and 162.6 explained that treatment with NaOH increases the galacturonic acid
mg/g. When compared to the unmodified orange peels, the adsorption groups after hydrolysis of O methyl ester groups and increases metal
capacities were 4.2-, 4.6- and 16.5-fold for Pb2+, Cd2+ and Ni2+, sorption. In another study, conducted by Massocatto et al. [30], NaOH
respectively. An equilibrium was reached within 150 min at 30 ◦ C. FTIR modified banana peel showed better adsorption results when compared
spectrum of the biosorbent depicted that carboxyl and hydroxyl groups with HCl and H3PO4 for the removal of Pb2+ from aqueous solution. The
were present in abundance and would have assisted in adsorption of the NaOH modified banana peel had the maximum biosorption capacity of
metal ions onto the biosorbent surface. Overall, the adsorption capacity 90 mg/g and followed the Freundlich adsorption isotherm. It was also
increased significantly by grafting methyl acrylate on orange peel. This proved through desorption studies that the NaOH-modified banana peel
can be attributed to the introduction of additional carboxyl groups on most efficiently desorbed the lead ions with HCl as the desorbing agent.
the adsorbent surface. FTIR analysis confirmed the presence of hydroxyl, carbonyl, phosphate,
and carboxyl groups present on the biomass. It also showed the differ
5.2.5. Comparative studies of chemically modified biosorbents using ence in morphological structure before and after modification. Accord
various modifying agents ing to the peak intensities, banana peel modified with HCl gave the most
The effect of chemical modification on the sorption efficiency de drasticcalteration and suggested the presence of carboxyl anions.
pends on many factors such as the type of modifying agent, nature of the Morphological studies revealed that H3PO4 did not alter the surface
biosorbent material itself and the type of the ions being adsorbed significantly but there was a notable alteration in the structure of banana
[196,197]. Therefore, the outcome of chemical modification will be peels modified with NaOH and HCl. The surface showed irregularities in
different for each type of biosorbent. In a study conducted by Villen- the form of lamellar pore channel which may be attributed to the hy
Guzman et al. [94], various modifying agents such as HNO3, HCl, drolysis reaction of carbohydrates and fibers. Banana peel modified with
H3PO4, CaCl2, NH3 and NaOH were used to modify lemon peel for the NaOH also portrayed a rougher surface which is favourable for
18
Fig. 3. SEM images of raw lemon peel a) before and b) after Ni (II) biosorption and lemon peel modified with NaOH c) before and d) after Ni (II) biosorption.
Reprinted with permission from ref. [94]. Copyright 2019 Elsevier.
adsorption. Shuhaimen et al. [145] studied removal of copper ions from present on the biosorbent surface according to the results of FTIR
aqueous solution by papaya peels modified with NaOH and concluded analysis. Also, the pore volume and specific surface area were found to
that the hydroxyl and carboxyl groups on the papaya peel were involved be greater than NaOH treated cashew shell.
in the adsorption of copper ions. There were studies in which acid
treatment showed better results when compared to other base treat 5.2.6. Chemical modification of biosorbents using magnetic particles
ments. For example, in a study performed by Santos et al. [104], the Magnetic particles and nanoparticles have proven to increase the
authors investigated the effect of chemical modification on sugarcane sorption efficiency of biosorbents. Moreover, due to their magnetic
bagasse by citric acid, NaOH and citric acid with NaOH treatment on the properties, they can be easily separated after biosorption has taken
removal of lead ions from aqueous solution. Chemical modification by place. Peanut hull is an agricultural waste produced from the shelling
citric acid showed the best results. FTIR analysis conducted after process of graded peanuts. It was estimated that about 500,000 tonnes of
chemical modification indicated that carboxylic acid groups were pre peanut hull biomass are readily available annually. Due to its abundance
sent at a stretching vibration of 1730 cm− 1. In another investigation and high organic matter, it is a good candidate to be transformed into a
conducted by Nuithitikul et al. [112], the authors modified cashew biosorbent for heavy metals adsorption. It has been reported that the
nutshell with H2SO4, HNO3 and NaOH to remove Pb2+ from aqueous peanut body typically consists of proteins, polysaccharides and lipids.
solution. The authors noticed that the surface area increased signifi They consist of various metal binding functional groups such as hy
cantly after modification with H2SO4. The surface area after modifica droxyl, carboxyl and amine groups that participate in heavy metal
tion was 0.648 m2/g. The pore volume and mean pore diameter also binding [127,203]. However, to increase the adsorption efficiency and
increased after modification. Modification with H2SO4 also showed the physical characteristics of peanut-hull based biosorbents, researchers
best adsorption capacity of 8.30 mg/g whereas untreated cashew have applied various types of chemical modifications techniques in
nutshell showed the lowest adsorption capacity of 2.08 mg/g. It was order to improve the adsorption capacity of biosorbents. For example, in
reported by Esteghlalian et al. [202] that pre-treating biosorbents with a study conducted by Kucukcongar et al. [127], the authors produced a
dilute H2SO4 can lead to high reaction rates and enhanced cellulosic nanocomposite with peanut hull, iron (II) sulphate and iron (III) chlo
hydrolysis. Treatment with H2SO4 causes an increase in single O2 bond ride via co-precipitation method to study the removal of Ni2+ ions. FTIR
containing functional groups such as alcohols, phenols, esters etc. This analysis confirmed the presence of hydroxyl group on the surface of
was confirmed through FTIR analysis (sharp peaks at 1028, 1155 and modified (PH-Fe3O4 at 3324.71 cm− 1) and unmodified peanut hull (PH
1207 cm− 1). The significant increase in efficiency could be attributed to at 3303.05 cm− 1). However, after the biosorption of nickel ions took
the C–– O and C–O bonds formed after modification. In this study, place, the peak of the hydroxyl groups was not present anymore indi
cashew nutshell modified with HNO3 showed the next highest adsorp cating that this group may have been involved in the binding of heavy
tion capacity. When compared to NaOH modified cashew nutshell, metals. Moreover, changes in the O–H, C–H, C–O and Fe–O peaks
HNO3 modified cashew nutshell had increased number of actives sites during the analysis proved their participation in the sorption process.
19
Additionally, SEM analysis of PH-Fe3O4 showed the presence of lignin, hydroxyl groups, litchi peels have the ability to adsorb heavy metals.
protein, cellulose, long thin fibers and active zones. After adsorption of These functional groups cause the surface of litchi peels to be negatively
nickel onto the nanocomposite, the number of occupied pores and par charged thereby promoting heavy metal uptake. It was reported by
ticles increased when compared to unmodified peanut hull due to the Jiang et al. [204], that magnetically modifying LP with Fe3O4 nano
adsorption of nickel ions and presence of iron oxide particles. Based on particles (MLP) enhanced the removal of Pb(II) from aqueous solution.
the SEM-EDX analysis performed on the PH-Fe3O4 nanocomposite for The functional groups of both LP and MLP were analysed through FT-IR
elemental analysis, it was concluded that the nanocomposite consisted spectra. The adsorption peaks confirmed the presence of hydroxyl,
of a high percentage of iron, carbon and oxygen. The presence of iron amino, and carbonyl groups. Notably, the introduction of Fe3O4 nano
oxide was also confirmed through SEM-EDX. The percentage of iron particles onto the litchi peels did not alter the active groups present on
oxide increased from 0.21% in peanut hull to 15.94% in PH-Fe3O4 the biosorbent surface. The magnetic litchi peels were of super
indicating the effect of PH modification. The surface area of the nano paramagnetic nature according to the saturation magnetization curve
composite material was analysed through BET method. The surface area which also confirms the magnetization of the litchi peels. Isotherm
was found to be 37.44 m2/g. In this study, the native peanut hull orig studies resulted in a high correlation coefficient value for both
inally consisted of metal binding functional groups. Further modifica Freundlich and Langmuir model. The adsorption kinetics followed a
tion of the peanut hull by incorporating magnetic nanoparticles, pseudo-second-order model with a correlation factor of 0.9999 which
increased the surface area, added more actives sites and functional indicates that the adsorption took place mainly through chemisorption.
groups to the biosorbent, thereby improving the adsorption efficiency. As depicted in Fig. 4, separation studies showed that sedimentation after
Similarly, Lichi peels (LP) are an abundantly available agricultural adsorption in the presence of magnetic field occured rapidly. Thus, it can
waste with great heavy metal biosorption potential. Due to the presence be concluded that the presence of a magnetic field can provide quick and
of functional groups such as amino groups, carboxyl groups and efficient solid-liquid separation.
Fig. 4. Analysis of LP and MLP separation from a homogenized solution. a) The separation process of LP from homogenized solutions only under the action of
gravity. b) The separation process of MLP from homogenized solutions only under the action of gravity. c) The separation process of MLP from homogenized solutions
with the application of an external magnetic field.
Reprinted with permission from ref. [92]. Copyright 2015 Elsevier.
20
Pengsaket et al. [161] investigated the removal of Cu2+ by using on the external surface of the biosorbent by the non-porous nano
magnetically modified pomelo peel with Fe3O4 magnetic nanoparticles adsorbent present in the modified wheat straw. The unmodified wheat
(MNPs-PP). Co-precipitation method was used to synthesis the MNPs-PP straw only had micropores where the heavy metals could be adsorbed.
nanocomposite material by varying different ratios by weight (2:1, 2:2, Most of the biosorption process took place on the external surface, thus
2:4, 2:5, and 2:6). The sorption results showed that as the amount of all the metal binding functional groups were present on the exterior of
pomelo peel increased in the composite material, the sorption of Cu2+ the biosorbent. The MSW showed a superparamagnetic behaviour which
also increased. It was concluded that the MNPs-PP showed higher means that it can be separated easily with application of an external
adsorption capacity when compared to magnetic nanoparticles by itself. field. Spent coffee grains consist of materials such as polyhydroxy,
Among the magnetically modified pomelo peel ratios, MNPs-PP (2:6) polyphenol and tannin that can adsorb heavy metals [205]. It was re
achieved maximum adsorption of 8 mg/g. The adsorption equilibrium ported by Edathil et al. [87] that modifying coffee waste with Fe3O4
was reached at the 20–40-min mark. The inner pomelo peel contains nanoparticles via single pot co-precipitation enhanced the biosorption
polysaccharide that consist of many hydroxyl groups. It can be derived capacity of Pb2+ ions. There is a possibility of agglomeration of magnetic
that the adsorption process occurred due to the ion exchange between nanoparticles may occur but the presence of tannin can prevent this
the H+ present in the hydroxyl group and Cu2+ ions. from taking place. The modified coffee waste was porous, wrinkled and
had an entangled fibrous network. The structure also showed a slight
–mFeOH + Cu2+ = − (Fe–O)mCu(2− m)+
+ mH+ (5) increase in the heterogeneity of the biosorbent. A heterogeneous surface
Morphological studies of the MNPs-PP nanocomposite revealed that in favourable for biosorption to take place [158]. The maximum bio
the adsorption mechanism of Cu2+ occurred through ion exchange due sorption capacity obtained was 41.15 mg/g at a pH value of 7.3 and
to the presence of (-OH) functional group on the surface of the bio temperature of 25 ◦ C. The pH at the point of zero charge was found to be
sorbent. Separation studies were conducted by using an external mag 3.65 which indicates the surface charge of the biosorbent was negative
netic field which resulted in easy and quick settling of the Cu2+ and deemed favourable for adsorbing the positively charged lead ions
embedded in the MNP-PP. López-Téllez et al. [101] synthesised iron [92]. Upon application of data into the intraparticle diffusion model, it
oxide nanorods in orange peels to study the reduction of chromium (VI) was concluded that biosorption took place in 3 stages. In the first stage,
from aqueous solution. Constituents of orange peel such as cellulose, the adsorption rate was due to electrostatic forces between adsorbent
hemicellulose and lignin components are naturally occurring reducing surface and the adsorbate, the second stage was attributed to intra
agents. These components aid in the formation of iron and/or iron oxide particle diffusion where the adsorbate enters the pores of the adsorbent
nanorods from iron ions. The biosorbent had a maximum adsorption and the third stage is when equilibrium was achieved as a result of
capacity of 7.44 mg/g which is much higher when compared to reduced number of active sites. Thermodynamic studies indicated that
adsorption via unmodified orange peel that achieved an adsorption ca the process was spontaneous and endothermic in nature.
pacity of 1.9 mg/g. The adsorption mechanism suggested by the authors According to the above discussion, it can be concluded that chemical
is a redox reaction between hydroxyl groups and iron ions. Langmuir modification enhances biosorption performance. The enhancement
isotherm model was found to be the best fit adsorption isotherm. This usually occurs due to introduction of new or more functional groups on
means the adsorption was homogenous and underwent a monolayer the surface of the biosorbent which will facilitate mechanisms such as
formation. Costa et al. [143] investigated the sorption performance of ion exchange, complexation, redox reactions etc., removing compounds
magnetized coconut fiber for the removal of Cr(VI) from aqueous solu or groups that block potential active sites on the biosorbent, increasing
tion. At a pH of 2 and all other experimental factors at optimal condi the available surface area for biosorption to take place, increasing the
tions, the sorption capacity of the magnetized coconut fiber and natural porosity and heterogeneity of the surface. Many researchers used
coconut fiber was 87.38 mg/g and 23.87 mg/g, respectively. The process various modifying agents, each of which gave different properties and
attained equilibrium within 20 min. The magnetized coconut fibers degree of improvement. More studies on the interactions between
showed a 4 times higher sorption capacity than natural fibers. The pH at modifying agent and biosorbent will give a better understanding to
the point of zero charge was 3.19 for the natural fiber and 3.53 for the further improve the biosorption efficiency in an adsorption system.
magnetized fiber. Moreover, SEM analysis revealed that the natural fiber
was a porous material with plenty of pores and tubes on the surface of
5.3. Factors effecting biosorption
the biosorbent. Whereas, in the case of the magnetized coconut fiber,
smaller pore diameter was seen. There was a decrease in surface porosity
The biosorption process is greatly dependent on factors such as pH,
as pores were replaced by iron nanoparticles which acted as active sites
initial metal ion concentration, adsorbent dose, temperature and contact
for sorption. The SEM images also showed aggregates along the fiber
which aided in the increase of the adsorption capacity. There was also a
decrease in the amorphous nature of the biosorbent after the introduc Table 8
Summary of common effects of pH, biosorbent dose, initial metal concentration,
tion of crystalline magnetite onto its surface. Similarly, Haghighat and
contact time and temperature according to the studies discussed in this section
Ameri [35] also used iron nanoparticles to modify wheat straw (WS) to
[35,113,117,127,131].
synthesise a nano magnetic wheat straw (MWS) biosorbent for the
Factors effecting Common results seen in research papers
sorption of lead. Native wheat straw consists of many hydroxyl groups
biosorption
that be chemical reaction sites. These sites are where Fe3O4 iron parti
cles can be adsorbed and form Fe3O4 crystals. The FTIR spectra pH Sorption is generally seen to reduce at low due to
competition between metal ions and H+ ions. Sorption is
confirmed the presence of bonded hydroxyl group at broad peaks at seen to also reduce/stay constant at high pH due to
3346.28 cm− 1 in the native wheat straw. Other peaks on the spectra hydroxide formation. Maximum biosorption is commonly
depicted the carbonyl group stretching from aldehydes and ketones at reported in a pH range of 3–6.
1733.86 and 1658.38 cm− 1, stretch vibration of C–O from the hydroxyl Biosorbent dose Initially, the sorption is seen to increase due to availability
of numerous active sites after which sorption reduces.
group at 1427 cm− 1, stretch vibration of C–O in phenols at 1253.06
Initial metal ion Higher sorption capacity is seen at lower metal
cm− 1, the C–O band at 1054 cm− 1 depicting the lignin structure of the concentration concentration.
wheat straw. The modified wheat straw showed a maximum biosorption Contact time Sorption is typically rapid in the first ~30–120 min after
capacity of 50.76 mg/g whereas the unmodified wheat straw showed a which it reaches equilibrium.
maximum biosorption capacity of 41.15 mg/g. The increase in bio Temperature Depending upon thermodynamics of the biosorption
process, sorption is seen to increase in endothermic
sorption after modification was attributed to the sorption that occurred
processes and reduce in exothermic processes.
21
time and competing metal ions. Therefore, it is necessary to find the adsorb lead ions on nano magnetic wheat straw, the adsorption capacity
optimum conditions for the adsorption process. Table 8 shows some reduced as the pH decreased. This was attributed to clash between the
typical results seen in studies on biosorption using various agricultural competitive H+ ions and Pb(II) ions for adsorption on the active sites or
waste-based biosorbents. The following sections will discuss the effect of functional groups. The pH at the point of zero charge was found to be 2.1
these factors according to various studies conducted using agricultural and 2.6 for wheat straw and modified wheat straw, respectively.
wastes-based biosorbents. Therefore, it can be concluded that the surface of the modified bio
sorbent adsorbent was positively charged at pH < 2.6. The adsorption of
5.3.1. Effects of pH on biosorption cations is known to be best at a pH value great than the pH at the point of
In an adsorption process, the pH value is of great importance as it is zero charge which explains the increase in adsorption capacity above a
the driving force for the exchange of H+ ions with the heavy metal ions. pH value of 2.1 and 2.6. Also, the increase in pH value may have led to a
It is an essential factor that helps to determine the state of ionization of more negatively charged adsorbent surface which favours adsorption. It
functional groups present on the biosorbent surface [121]. In Table 9, was reported by Jiang et al. [204] that at a pH higher than the pH at the
the optimum pH for various agricultural waste-based adsorbents along point of zero charge, higher adsorption capacity was achieved. The
with the maximum adsorption capacities and experimental conditions authors found that the optimum pH for adsorption of Pb2+ ions by
such as contact time (CT), equilibrium contact time (Te), temperature magnetic litchi peels was 6, above which Pb(OH)2 would form. Cationic
(T), initial metal concentration (Co) and dosage (D) are listed. species are favourably adsorbed at a pH greater than the pH at the point
In a study conducted by Kucukcongar et al. [127], the authors found of zero charge and vice versa. Therefore, the authors concluded that a
that the removal efficiency of nickel increased from a pH range of 2–6 pH of 6 would give the best results. In general, in most adsorption
and remained at a constant value of 78% at a pH value greater 6. At studies, the optimal pH value was 3–6.
lower pH, due to the competition between H+ ions and Ni2+ ions, there is
a reduction in removal percentage whereas at a higher pH, deprotona 5.3.2. Effects of biosorbent dose or mass
tion is the cause of increase in the removal percentage. Similar trends An increase in biosorbent dosage or mass can decrease the bio
were noticed by various authors. For example, Sobhanardakani and sorption capacity due to reduced surface area, agglomeration of parti
Zandipak [110] studied the effect of pH on modified rice husk to remove cles, electrostatic interactions, less mixing, inaccessibility to solute and
Ni2+and Cd2+ ions form aqueous solution. The authors reported that in a lack of active sites [31,121,206]. In Table 10, the optimal adsorbent
pH range of 1–4, the percentage removal for Ni2+ and Cd2+ increased dosage (D), maximum adsorption capacities and experimental condi
from 25% to 93.5% and from 16% to 85%, respectively. The highest tions such as contact time (CT), equilibrium contact time (Te), temper
adsorption was achieved at a pH value of 4. The increase in sorption on ature (T), initial metal concentration (Co) and pH are listed. For
the modified rice husk from pH 1–4 can be attributed to the hydrolysis of example, Rosales et al. [117] varied the biosorbent mass from 0.3–1.5 g
the Ni2+and Cd2+ ions. At pH values lower than 4, the Ni2+and Cd2+ ions for the removal of hexavalent chromium at an initial concentration of
may be competing with the H+ ions for the available active sites during 35 mg/L. The maximum percentage removal of chromium (VI) was
the adsorption process. Therefore, a low removal percentage is ach 99.5% at a biosorbent mass of 1 g. The authors reported that an increase
ieved. However, at a higher pH value, due to the low concentration of in removal efficiency up to 1 g could be due to the availability of large
the H+ ions, there will be no competition with the Ni2+and Cd2+ ions. number of active sites on the surface of the biosorbent. However, the
Therefore, the removal percentage was higher. decrease in removal efficiency from 1 to 1.5 g biosorbent mass could be
It has been reported in various studies that the maximum biosorption due to the partial aggregation of the biosorbent. In another study,
takes place between the pH of 3–6 [15,26,110,145]. For example, Kucukcongar et al. [127] reported that upon increasing the dosage of
Shuhaimen et al. [145] used modified Carica papaya peels for the magnetic peanut hull for the removal of nickel ions, there was an in
removal of Cu2+ ions. The results showed that at a lower pH, the removal crease in removal percentage but there was a decrease in adsorption
percentage was only 17%. The low removal percentage was attributed to capacity. Similarly, Basu et al. [120] also reported comparable results
functional groups on the biosorbent being in a protonated state which when they increased the dose of cucumber peel biosorbent for the
will repel against other species with the same charge. There will be removal of cadmium. They reported that at a higher dosage of the bio
competing H+ ions that will occupy the active sites. However, at a higher sorbent, the percentage removal increased until a certain amount after
pH, deprotonation will occur, forming negative charges and thereby which the percentage removal decreased due to the presence of exces
attracting the cationic metal ions to form bonds with them. The highest sive active sites in comparison to the amount of heavy metal ions. It
removal percentage was 75% at a pH value of 3. In another study by could also be attributed to the electrostatic forces among the adsorbent
Feng et al. [88], the optimum pH was found to be in the range of 3–6. cells and due to the interference in between the active sites of the bio
The authors varied the pH of the solution from 2 to 7 for the adsorption sorbent. Jiang et al. [204] also noticed similar results and concluded that
of Pb2+, Cd2+ and Ni2+ ions from aqueous solution on modified orange a litchi peel dose of 5 g/L was the optimum dosage for the removal of
peel. The authors found that the lowest adsorption occurred at a pH Pb2+. At a higher dose, the removal efficiency decreased because the
value of 2 and increased as the pH increased up to a value of 5.5. The adsorbent formed aggregates and also because of the reduction in
decrease in sorption was attributed to the presence of competing Hþ ions available surface area for adsorption. On the contrary, Sobhanardakani
at lower pH. At a higher pH, the availability of larger number of ligands and Zandipak [110] increased the mass of modified rice husk from 0.08
bearing negative charge will favour the adsorption of metal cations. to 0.3 g for the removal of Ni2+and Cd2+ ions. The results of their study
Similarly, the optimum pH was 4 in a study conducted by Pan showed that there was an increase in removal percentage from 50% to
neerselvam et al. [132], in which the authors investigated the removal of 93.5% for Ni2+ and 33.5% to 85.5% for Cd2+. The authors attributed the
Ni2+ ions using magnetically modified tea waste. When the authors increase in the removal percentage to the availability of larger number
increased the pH from 2 to 4, the adsorption capacity increased. At a pH of active sites and increase in surface area. Similarly, another study
value greater than 4, the adsorption capacity stayed constant. Ay et al. conducted by Abbaszadeh et al. [207], the authors varied the mass of
[135] also reported an optimum pH of 5 when the authors used apple magnetically modified papaya peel waste that was used to remove Pb2+
juice residue to remove lead ions from aqueous solution. On varying the ions from aqueous solution. It was found that the adsorption efficiency
pH of the solution, the authors saw low biosorption at pH levels of increased upon increasing the mass of the biosorbent from 10 to 50 mg
1.5–2.5. due to the availability of active sites but there were no significant
The effect of pH on the biosorption process can also be studied in changes in the adsorption efficiency from 50 to 200 mg. The lack of any
terms of pH at the point of zero charge (pHpzc) [121]. For example, further increase in adsorption efficiency could be due to the system
Haghighat and Ameri [35] reported that during a study conducted to reaching equilibrium [97].
22
Table 9
Optimum pH for various agriculture based adsorbents.
Biosorbent Metals removed Maximum removal (mg/g) % Removal Range pH Experimental conditions Reference
2þ
Coffee waste Pb 41.15 – 2–12 7.3 Co = 10 mg/L [87]
D = 0.010 g
CT = 240 min
T = 25 ◦ C
Orange peel Pb2þ 476.1 – 2–7 5.5 T = 30 ◦ C [88]
Cd2þ 293.3 D = 0.05 g
Ni2+ 162.6 CT = 3 h
Banana peel Cr(VI) 6.1728 96 1–10 3 T = 30 ◦ C [85]
Banana peel Mn2þ 5.7306 94 1–10 8 T = 30 ◦ C [90]
D=4g
Orange peel Pb2þ 164 – 2–6 5 CT = 2 h [91]
Zn2+ 80 D = 5 g/L
Co (Pb2+) = 100 mg/L
Co (Zn2+) = 50 mg/L
Orange peel Cu2þ 70.73 – 2–7 5 T = 298 K [32]
Pb2þ 209.8 5.5 D = 0.10 g
Zn2+ 56.18 5.5 T = 120 min
Litchi peels Pb2+ 78.74 – 3–8 6 Co = 50 mg/L, [92]
T = 25 ◦ C
D = 0.25 g
CT = 3 h
Pineapple peel Cd2þ 42.10 – 1–7 4 D = 0.2 g [93]
Pb2+ 28.55 T = 25 ◦ C,
Co = 100 mg/L
Lemon peel Ni2+ 36.74 – 2–6 5 Co = 100 mg/L [94]
D = 10 g/L
CT = 3 h
Banana peel Pb2þ 89.286 – 1–9 7 Co = 10 mg/L [95]
Cu2+ 5.720 9 D = 0.5 g
Lemon peel Cd2+ – 93.3 2–6 4 – [162]
Lemon peel Ni2+ – 90.1 2–6 6 – [162]
Papaya leaves Pb2+ 284.35 – 3–8 4 Co = 30 mg/L [96]
D = 0.1 g
CT = 15 min
Petai peel Pb2+ 36.01 – 3–8 5 Co = 50 mg/L [96]
D = 0.1 g
CT = 15 min
Papaya peel Cu2+ – 79 1–9 3 D = 0.9 g [145]
CT = 1 h
Co = 10 mg/L
Banana peel Cd2þ 27.77 – 2–9 6 CT = 60 min [97]
Cr(III) 38.46 T = 28 ◦ C
Zn2+ 9.52
Kiwi Cd2þ 15.87 – 2–9 6 CT = 60 min [97]
Cr(III) 41.66 T = 28 ◦ C
Zn2+ 37.03
Tangerine Cd2þ 17.54 – 2–9 6 CT = 60 min [97]
Cr(III) 47.61 T = 28 ◦ C
Zn2+ 38.41
Tomato waste Pb2+ 152 – 2–10 4 CT = 1 h [98]
Co = 20 ppm
2+
Pomelo peel Pb – 96.12 2.5–7 3.5–5.5 Co = 100 mg/L [163]
CT = 100 min
Peanut husk Ni2+ 0.1473 – 4.5–7.5 6.5 T = Room temp [100]
D = 2.5 g/L
Co = 0.5 mg/L
Peanut husk Cr(VI) 33.11 – 2–12 2 Co = 25 ppm [101]
CT = 24 h
2þ
Sugarcane bagasse Cd 33.2 – 3–6 6 [102]
Pb2+ 116.7
Sugarcane bagasse As(III) – 98.9 – 6 – [139]
Sugarcane bagasse Zn2þ – 74.91 2–12 6–8 D = 0.5 g [103]
Cr(IV) 76.54 Co = 50 mg/L
CT = 120 min
T = 30 ◦ C
Wheat straw Pb2+ 50.76 – 2–6 5 Co = 400 mg/L [35]
pH = 5
D = 32 g/L
CT = 30 min
Sugarcane bagasse As(III) 28.57 – 2–7 7 Co = 500 ppb [106]
As(V) 34.48
Sugarcane bagasse As(V) 22.1 – 2–10 4 Co = 50 ppm [107]
T = 22 ± 2 ◦ C
Sugarcane bagasse – 3–7 5.5 [108]
23
Biosorbent Metals removed Maximum removal (mg/g) % Removal Range pH Experimental conditions Reference
Co2þ 56.1 Co = 0.79 mmol/L

Cu2þ 93.5 T = 25 ◦ C
Ni2+ 93.2 D = 0.2 g/L
Rice husk Cd2þ 45.5 – 1–6 4 Co = 60 mg/L [110]
Ni2+ 55.5 CT = 45 min
D = 0.3 g
T = 25 ◦ C
Rice husk Cd2+ 137.16 – 3–7 7 Co = 25, 10, 5 mg/L [70]
Cashew nut shell Cu2+ 48.05 – 2–8 6 Co = 40 mg/L [111]
D = 2 g/L
Te = 30 min
T = 30 ◦ C
Groundnut hull Cr(VI) 131 – 1–8 2 CT = 120 min [113]
T = 28 ◦ C
Citrus lemon peels U(VI) 24.39 – 1–12 8 D = 100 mg [114]
T = 25 ◦ C
Te = 1 h
Garlic peel Pb2+ 109.05 – 1–7 5 – [115]
Musk melon peel Pb2+ 167.8 – 1–7 4.5 D = 0.080 g [116]
Co = 1.0 mmol/L
CT = 120 min
T = 303 K
Grapefruit peel Pb2+ 12.73 – 2–8 5.3–6.5 D=1g [118]
Grapefruit peel Cd2þ 42.09 – 2–10 5 Co = 50 mg/L [119]
Ni2+ 46.13 T = 25 ◦ C
Lemon peel Co2+ 35.71 – 2–7.5 6 D = 2 g/L [121]
Co = 100 mg/L
CT = 6 h
T = 30 ◦ C
Orange peel Cd2+ 125.63 – – 5–5.5 – [33]
Orange peel As(V) 43.69 95 2–8 5.5 Co = 100 μg/L [124]
D = 0.25 g
CT = 20 min
T = 25 ◦ C
Cassava peel Hg2+ – 72.98 2–6 6 – [125]
Lemon peel Hg2+ – 49.83 2–6 6 – [125]
Corncob Pb2+ 0.2095* – 2–6 5 Co = 0.1 mmol/L [126]
Coconut fiber Cr(VI) 87.38 <90% 1–13 2 Co = 100 mg/L [143]
D = 500 mg
T = 28 ◦ C
Peanut hull Ni2+ 8.63 – 2–6 6 T = 25 ◦ C [127]
Banana peel Pb2+ 90 – 3–7 5 D = 0.5 g [30]
Coconut pith Ni2+ 24.39 – 2–10 6 T = 30 ◦ C [129]
Tea waste Pb2þ 153 – 2–8 6 – [131]
Cd2+ 222 7
Tea waste Ni2+ 38.3 – 2–7 4 T = 303 K [132]
Watermelon rind As(V) – 98 3–10 4.6 Co = 4 mg/L [134]
As(III) – 99 8.2 D = 1 g/L
T = 20 ◦ C
Punica granatum L. Pb2+ 371.36 1–6 5.5 T = 20 ◦ C [135]
Acid modified banana stalk Pb2+ 13.53 96.76 4–8 8 T = 30 ◦ C [31]
Based modified banana stalk Pb2+ – – 4–8 8 T = 30 ◦ C [31]
Banana stem Hg2+ 132.25 – 2–9 7 Co = 25 mg/L [138]
*
Unit: mmol/g.
5.3.3. Effect of initial metal ion concentration the ratio of available active sites to the heavy metal is large whereas at a
Initial metal ion concentration is another factor that can influence high initial metal ion concertation, this ratio is low because most of the
the biosorption capacity of a biosorbent. Many studies have reported active sites are saturated. Therefore, low biosorption efficiency would be
that low initial metal ion concentration gives higher biosorption ca expected [203,208]. A similar trend was observed by Haghighat and
pacity. In Table 11, the optimum initial metal ion concentration (Co) for Ameri [35] when they studied the effect of Pb2+ concentration on the
various agriculture waste biosorbents along with their maximum removal efficiency of modified and unmodified wheat straw. The results
adsorption capacities and experimental conditions such as contact time showed that at a lower metal ion concentration, the removal efficiency
(CT), equilibrium contact time (Te), temperature (T), dosage (D) and pH was higher. The authors varied the lead concentration from 10 to 1000
are listed. mg/L. They found that at a low concentration of 10 mg/L the removal
For example, a study was conducted by Kucukcongar et al. [127] in efficiency of modified and unmodified wheat straw was 89.3% and 88%,
which the authors varied the concentration of nickel from 10 to 100 mg/ respectively. At a lead concentration of 1000 mg/L, the removal per
L to investigate its effect on the adsorption efficiency of magnetically centages were reduced to 18.9% for modified wheat straw and 16% for
modified peanut hull. It was seen that the removal efficiency decreased unmodified wheat straw. This could be because the adsorption of lead
with the increase in metal concentration. The removal efficiency at 10 occurred at higher energy sites when the concentration of lead was low.
mg/L and 100 mg/L was 82.8% and 32.6%, respectively. This could be On the other hand, when the concentration of lead is high, adsorption
attributed to the lack of active sites available for the nickel ions when the may occur on lower energy sites. An increase in metal concentration also
metal concentration is increased. At a lower initial metal concentration, results in the decrease of initial rate of external diffusion and an increase
24
Table 10
Optimal adsorbent dosage for various studies using agriculture waste based biosorbents.
Biosorbent Metals Range Optimum dose/remarks Experimental Maximum removal Reference
removed conditions (mg/g)
Coffee waste Pb2þ 0–0.030 g 10 mg Co = 10 and 100 mg/L 41.15 [87]

CT = 30 min
pH = 7.3
T = 25 ◦ C
Orange peel Cd2þ 0.1–2 g Initially there was an increase in R%. At adsorbent dosage T = 25 ◦ C 13.7 [89]
Cu2þ >0.1 g pH = 5 15.27
Pb2+ for Pb(II), >0.5 g for Cu(II) and >0.8 g for Cd(II) the R% is 73.53
very low
Banana peel Cr(VI) 1–5 g/L 4 g/L Co = 400 mg/L 6.1728 [85]
pH = 4
CT = 60 min
Banana peel Mn2þ 1–5 g/L 4 g/L – 5.7306 [90]
Litchi peels Pb2+ 1.0–20.0 g/L 5 g/L pH = 6 78.74 [92]
CT = 3 h
Lemon peel Ni2+ 1–20 g/L 5 g/L Co = 100 mg/L, 36.74 [94]
pH = 5
2þ
Banana peel Pb 0.1–0.9 g 0.9 g Co = 10 mg/L 89.286 [95]
Cu2+ T = 30 ± 2 ◦ C 5.720
Papaya leaves Pb2+ 0.1–1 g 0.1 g pH = 4 284.35 [96]
Co = 5400 mg/L
CT = 15 min
Petai peel Pb2+ 0.1–1 g 0.1 g pH = 5 36.01 [96]
Co = 590 mg/L
CT = 15 min
Papaya peel Cu2+ 0.1–0.9 g 0.9 g Co = 10 mg/L – [145]
Banana peel Cd2þ 0.1–2.0 g 2 g/L Co = 10 mg/L 27.77 [97]
Cr3þ pH = 6 38.46
Zn2+ 9.52
Kiwi Cd2þ 0.1–2.0 g 2 g/L Co = 10 mg/L 15.87 [97]
Cr3þ pH = 6 41.66
Zn2+ 37.03
Tangerine Cd2þ 0.1–2.0 g 2 g/L Co = 10 mg/L 17.54 [97]
Cr3þ pH = 6 47.61
Zn2+ 38.41
Tomato waste Pb2+ 0.0125– 0.100 g – 152 [98]
0.1250 g
2+
Pomelo peel Pb 5–15 g/L 15 g/L Co = 100 mg/L – [163]
CT = 100 min
pH = 3.5
Peanut husk Ni2+ 0.5–5.5 g/L 2.5 g/L pH = 6.5 0.1473 [100]
T = room temp
Sugarcane As(III) 0.5–10 g/L 10 g/L CT = 60 min – [139]
bagasse Co = 0.380 mg/L
2þ
Sugarcane Zn 0.1 g–0.9 g 0.9 g pH = 6 – [103]
bagasse Cr(IV) T = 30 ◦ C
CT = 120 min
Wheat straw Pb2+ 0.01–1.0 g 0.8 g and Co = 400 mg/L 50.76 [35]
pH = 5
CT = 30 min
Sugarcane As(III) 0.5–25 g/L >98% R using 0.3 g CT = 2 h 28.57 [106]
bagasse As(V) pH = 7 34.48
Sugarcane As(V) 0.1–0.25 g 0.25 g Co = 2 mg/L 22.1 [107]
bagasse pH = 4
T = 23 ◦ C
Rice husk Cd2þ 0.1–1 g 1g Co = 60 mg/L pH = 4 45.5 [110]
Ni2+ CT = 45 min, T = 25 55.5
◦
C
Rice husk Cd2+ 0.1–0.7 g/L 0.1 g/L Co = 50 mg/L 137.16 [70]
CT = 120 min
T = 288 K
Cashew nut shell Cu2+ 0.5–3.0 g/L 2 g/L Co = 40 mg/L pH = 48.05 [111]
5.0
Te = 30 min, T = 30
◦
C
Groundnut hull Cr(VI) 10–50 mg Increase in R% from 5 to 40 mg T = 28 ◦ C 131 [113]
CT = 120 min
Citrus lemon U(VI) 25–500 mg 100 mg Co = 50 mg/L 24.39 [114]
peels pH = 8
T = 25 ◦ C
Te = 1.0 h
Garlic peel Pb2+ 1–100 mg 60 mg Co = 150 g/L 109.05 [115]
Musk melon peel Pb2+ 1.0–5.0 g/L 0.080 g Co = 0.5 mmol/L 167.8 [116]
pH = 4.50
25
Biosorbent Metals Range Optimum dose/remarks Experimental Maximum removal Reference
removed conditions (mg/g)
CT = 120 min T =
303 K
Grapefruit peel Cr(VI) 0.3–1.5 g 1g Co = 35 mg/L 39.0628 [117]
Grapefruit peel Pb2+ 10 g/L– 15 g/ 10 g/L CT = 1.5 h 12.73 [118]
L T = room temp
Grapefruit peel Cd2þ 0.02–0.1 g 0.1 g Co = 50 mg/L 42.09 [119]
Ni2+ T = 25 ◦ C 46.13
Cucumber peel Cd2+ 0.01–0.2 0.1 g pH = 5 0.998* [120]
T = 30 ◦ C
Co = 50 mg/L
Lemon peel Co2+ 1–2 g/L 2 g/L Co = 100 mg/L 35.71 [121]
pH = 6
CT = 6 h
T = 30 ◦ C
Orange peel Cu2+ 1–6 g/L 5 g/L Co = 50 mg/L pH = 40.37 [123]
5.3
Peanut hull Ni2+ 2–11 g/L 4 g/L T = 25 ◦ C 8.63 [127]
Green tea waste As(III) 0.1–0.6 g Adsorption capacity of arsenic decreased with increased pH = 3 0.4212 [128]
adsorbent dosage T = 33 ◦ C
Co = 5 mg/L
Green tea waste Ni2+ 0.1–0.6 g Adsorption capacity of nickel decreased with increased Co = 5 mg/L 0.3116 [128]
adsorbent dosage pH = 3
T = 33 ◦ C
Coconut pith Ni2+ 0.25–3 g/L 2.0 g/L pH = 6 24.39 [129]
Te = 120 min
2þ
Tea waste Pb 0.01–0.04 g R% of both metals increased with adsorbent dose pH (Pb2+) = 6 153 [131]
Cd2+ pH (Cd2+) = 7 222
Tea waste Ni2+ 0.40–0.60 g 0.60 g T = 303 K 38.3 [132]
Watermelon rind As(V) 1–16 g/L 1 g/L T = 20 ◦ C – [134]
As(III) CT = 2 h –
D = 5 mg/L
Corn cob Cu2+ 1–3 g Cu2+ = 1.5 g T = 303 K 75.76 [166]
Zn2+ Zn2+ = 1 g Co = 100 ppm 63.93
Black gram husk Cr(VI) 0.05–0.5 mg 0.5 g/L CT = 180 min 215.27 [136]
*
Unit: mmol/g.
in intra-particles which could reduce the biosorption capacity [97]. 34.36 kJ/mol and 14.12 kJ/mol for lead and cadmium, respectively.
Sharma and Bhalerao [209] also noticed similar results when they This explains that the process was endothermic in nature. In another
varied Cr(VI) concentrations to investigate the removal efficiency by study, the adsorption of hexavalent chromium on modified groundnut
banana peels. The authors varied the metal concentration from 5 to 250 hull was studied by increasing the temperature from 30 to 60 ◦ C. The
mg/L and found that the removal efficiency decreased upon increasing results revealed that the adsorption capacity decreased as the temper
the metal concentration. Shakoor et al. [134] varied As(III) and As(V) ature increased from 30 to 60 ◦ C. This indicates that the process was an
concentrations to investigate its effect on the adsorption capacity of exothermic process [113]. Similarly, Qu et al. [70] saw a decrease in
modified watermelon rind. The authors reported that the maximum sorption with an increase in temperature indicating that the process was
adsorption took place at a concentration of 4–5 mg/L and any further exothermic. It was reported by Joshi et al. [131] that increasing the
increase in concentration did not enhance the adsorption capacity. temperature enhanced the diffusion and interaction between metal ions
Similarly, Ratan et al. [129] varied nickel concentration from 0 to 60 and the active sites on the biosorbent. The authors saw an increase in
mg/L to study its effect on removal efficiency by modified coconut coir Cd2+ and Pb2+ sorption on SiO2-Teawaste nanocomposites when the
pith. The authors noticed a decrease in removal efficiency with the in temperature was increased from 30 ◦ C to 50 ◦ C. The sorption percentage
crease in initial metal concentration. This could be because at lower of Cd2+ increased from 95.2% to 99.7% and the sorption percentage of
efficiencies, plenty of unoccupied active sites are available for bio Pb2+ increased from 89.8% to 95.7%. Similar results were obtained in a
sorption to take place [198]. study conducted by Sharma and Bhalerao [209] in which the authors
investigated the effect of Cr(VI) sorption on banana peels by increasing
5.3.4. Effect of temperature the temperature from 20 ◦ C to 40 ◦ C. The removal of Cr(VI) increased
Temperature in a biosorption process plays a crucial role in the up from 41.69% to 49.69% upon increasing the temperature and the ΔH
take of heavy metals. In Table 12, optimal temperature (T), maximum value was found to be positive. The process was endothermic in nature.
removal capacities, thermodynamic parameters and experimental con Moreover, the ΔG value was found to be negative and low which means
ditions such as contact time (CT), dosage (D) and pH are listed for that the driving force was high and could explain the higher biosorption
various agriculture-based adsorbents are listed. value.
Factors such as enthalpy (ΔH), entropy (ΔS), Gibbs free energy (ΔG)
are able to describe the enthalpy change, randomness and spontaneity of 5.3.5. Effect of contact time
the system. The enthalpy can determine if the process is endothermic or In various studies, it was reported that biosorption of heavy metals
exothermic. For example, a study was conducted to adsorb cadmium and takes place very quick at the initial stages of the process. This is
lead on spent grain [201]. Upon increasing the temperature, adsorption generally due to abundance of available active sites for the heavy metals
of lead and cadmium on spent grain increased. When the temperature to bind to. In Table 13, the optimum contact time for various agriculture
was increased from 15 ◦ C to 55 ◦ C, the sorption of cadmium increased waste based biosorbents has been listed along with the maximum
from 14.21 mg/g to 16.20 mg/g whereas as the sorption of lead removal capacities and experimental conditions such as adsorbent
increased from 27.8 mg/g to 36.68 mg/g. The ΔH value was found to be dosage (D), temperature (T), initial metal ion concentration (Co) and pH.
26
Table 11
Optimum initial metal ion concentration for various agriculture waste biosorbents.
Biosorbent Metals Range of initial Optimum Co Experimental Maximum % Reference
removed concentration conditions removal (mg/ Removal
g)
Coffee waste Pb2þ 0–100 mg/L 25 mg/L D = 0.010 mg 41.15 – [87]

CT = 30 min
pH = 7.3
T = 25 ◦ C
Banana peel Cr(VI) 100–600 mg/L 400 mg/L pH = 4 6.1728 96 [85]
T = 25 ◦ C
2þ
Banana peel Mn 100–600 mg/L 400 mg/L T = 25 ◦ C 5.7306 94 [90]
pH = 8
CT = 2 h
D=4g
Banana peel Pb2+ 2–10 mg/L 2 and 4 mg/L D = 0.5 mg 89.286 – [95]
Cu2+ 2 mg/L 5.720
Papaya leaves Pb2+ 0–7500 mg/L The sorption capacity increased with increasing pH = 4 284.35 – [96]
concentration of Pb(II) ions D = 0.1 g
CT = 15 min
Petai peel Pb2+ 0–7500 mg/L The sorption capacity increased with increasing pH = 5 36.01 – [96]
concentration of Pb(II) ions D = 0.1 g
CT = 15 min
Banana peel Cd2+ 5–100 ppm Removal decreased with an increase in the initial pH = 6 27.77 – [97]
Cr3+ concentration of the metal ions D = 0.5 g 38.46
Zn2+ 9.52
Kiwi Cd2+ 5–100 ppm Removal decreased with an increase in the initial pH = 6 15.87 – [97]
Zn2+ 37.03
Tangerine Cd2+ 5–100 ppm Removal decreased with an increase in the initial pH = 6 17.54 – [97]
Zn2+ 38.41
Pomelo peel Pb2+ 40–160 mol/L As the initial concentration of lead ion increased, the pH = 3.5 – 96.12 [163]
absorption rate was reduced CT = 100 min
2+
Peanut husk Ni 0.3–0.7 mg/L 0.3 mg/L D = 2.5 g/L 0.1473 – [100]
pH = 6.5
Sugarcane Zn2+ 20–100 mg/L Percentage adsorption of the metal ions increased with the T = 30 ◦ C – 74.91 [103]
bagasse Cr(IV) initial concentration from 20 mg/L to 40 mg/L and the 76.54
increase gradually decreased from 60 mg/L to 100 mg/L
Wheat straw Pb2+ 0–1000 mg/L 10 mg/L D = 4 g/L 50.76 – [35]
pH = 5
CT = 30 min
Sugarcane As(V) 10–300 ppm 300 ppm D = 0.2 g 22.1 – [107]
bagasse pH 4; 22 ± 2
CT = 3 h
Cashew nut Cu2+ 20 to 100 mg/L 20 mg/L pH = 5.0 48.05 – [111]
shell D = 2 g/L
Te = 30 min
T = 30 ◦ C
Garlic peel Pb2+ 1 to 200 mg/L 100 mg/L CT = 30 min 109.05 – [115]
pH = 5
D = 5 mg
Musk melon Pb2+ 0.1–1 mmol/L 1 mmol/L D = 0.080 g 167.8 – [116]
peel pH = 5.80
T = 303 K
Grapefruit Pb2+ 0–200 mg/L 100 mg/L – 12.73 – [118]
peel
Peanut hull Ni2+ 0–100 mg/L 82.8% nickel removal efficiency was achieved for 10 mg/L T = 25 ◦ C 8.63 – [127]
initial nickel content, but decreased to 32.6% for 100 mg/L
Coconut pith Ni2+ 0–60 mg/L 10 mg/L D = 2 g/L 24.39 – [129]
Removal of metal ion decrease with increase in nickel pH = 6
concentration CT = 2 h
Tea waste Pb2+ 10–100 mg/L Pb2+ and Cd2+ ions decrease from 94.70 to 75.64% and D = 0.03 g 153 – [131]
Cd2+ 94.10 to 86.93% with increase in metal ions pH = 7 222
concentrations T = 27 ◦ C
Tea waste Ni2+ 50–100 mg/L Removal efficiency increased from 90 to 96% with the D = 0.25 g 38.3 – [132]
increase of initial concentrations of nickel T = 303 K
CT = 3 h
Corn cob + Pb2+ 200–500 mg/L 400 mg/L – 2.230 – [133]
petai hull
Punica Pb2+ 145 mg/dm3–200 200 mg/dm3 pH = 5.5 371.36 [135]
granatum L. mg/dm3
Black gram Cr(VI) 50–500 mg/L Adsorption decreased with an increase concentration – 215.27 – [136]
husk
2+
Banana stem Hg 10–100 mg/L At higher initial concentration of metal ions an increase in T = 30 C
◦
132.25 – [138]
adsorption was observed CT = 1 h
27
Table 12
Optimal temperature and thermodynamic parameters for various agriculture waste based adsorbents.
Biosorbent Metals Range Optimum/Remarks Experimental Parameter Nature of Maximum % Reference
removed conditions reaction removal Removal
(mg/g)
Coffee waste Pb2þ 25–45 ◦ C Uptake capacity increased from C0 = 0 to 100 At 308 K Endothermic 41.15 – [87]
25 to 45 ◦ C mg/L ΔG◦ (kJ/mol)
D = 0.010 g CT = = − 24.011
30 min pH = 7.3 ΔH◦ (kJ mol/
L) = − 13.411
ΔS◦ (J/mol
K) = 121.592
Litchi peels Pb2+ 288–388 – pH = 6 At 288 K Exothermic 78.74 – [92]
K Co = 50 mg/L ΔG◦ (kJ/mol)
= − 7.13
ΔH◦ (kJ mol/
L) = − 5.16
ΔS◦ (J/mol
K) = 5.44
Pineapple Cd2+ 298 to – – At 298 K for Exothermic 42.10 – [93]
peel Pb2+ 323 K Pb2+ 28.55
ΔG◦ (kJ/mol)
= − 0.857
ΔH◦ (kJ mol/
L) = − 63.530
ΔS◦ (J/mol
K) = − 75.017
At 298 K for
Cd2+
ΔG◦ (kJ/mol)
= − 3.499
ΔH◦ (kJ mol/
L) = − 26.089
ΔS◦ (J/mol
K) = − 217.66
Lemon peel Ni2+ 20–25 ◦ C Adsorption of metals has been – At 293 K Endothermic 36.74 – [94]
observed to increase with ΔG◦ (kJ/mol)
temperature = − 3.16
ΔH◦ (kJ mol/
L) = − 14.05
ΔS◦ (J/mol
K) = 58.74
Sugarcane As(III) 70–80 ◦ C Adsorption increased with the Co = 0.5 mg/L At 20 ◦ C Endothermic – 98.9 [139]
bagasse increase in temperature D = 10 g/L ΔG◦ (kJ/mol)
= − 763.305
ΔH◦ (kJ mol/
L) = 8030.49
ΔS◦ (J/mol
K) = 30.71
Sugarcane Zn2+ 30–60 ◦ C Adsorption increased with the D = 0.5 g – – – 74.91 [103]
bagasse Cr(IV) increase in temperature pH = 6 76.54
Co = 50 mg/L
CT = 120 min
Musk melon Pb2+ 303–323 Adsorption increased with the D = 0.080 g – – 167.8 – [116]
peel K increase in temperature pH = 5
2+
Grapefruit Pb 20–45 ◦ C Adsorption capacity increased pH = 5.3–6.5 – 12.73 – [118]
peel with increase in temperature D = 10 g/L
CT = 1.5 h
Co = 15–230 mg/
L
Lemon peel Co2+ 30 to 40 Increase in temperature from 30 D = 2 g/L – – 35.71 – [121]
◦
C to 40 ◦ C decreased the pH = 6
adsorption capacity by 5.76% CT = 6 h
Coconut coir Ni2+ 293–323 – – At 293 K Endothermic 24.39 – [129]
pith K ΔG◦ (kJ/mol)
= − 1.2019
ΔH◦ (kJ mol/
L) = 22.93
ΔS◦ (J/mol
K) = 82.92
Tea waste Pb2+ 30–50 ◦ C Removal of the Pb2+ and Cd2+ pH (Pb2+) = 6 – 153 – [131]
Cd2+ ions increased from 68.2% to pH (Cd2+) = 7 222
77.2% and 73% to 86% at 30, 40
and 50 ◦ C
Watermelon As(V) 20–45 ◦ C – D = 1 g/L At 20 ◦ C Endothermic – 98 [134]
rind As(III) Co = 4 mg/L ΔG◦ (kJ/mol) – 99
CT = 2 h = − 0.38 ±
28
Biosorbent Metals Range Optimum/Remarks Experimental Parameter Nature of Maximum % Reference
removed conditions reaction removal Removal
(mg/g)
0.12
ΔH◦ (kJ mol/
L) = 86.86 ±
12.21
ΔS◦ (J/mol
K) = 0.30 ±
0.06
Corn Cob Cu2+ 30–60 ◦ C 50 ◦ C D=1g – 75.76 89.2 [166]
Zn2+ R% for both heavy metals (i.e. Co = 100 ppm 63.93 89.3
Cu(II) and Zn(II)) decreased at a
temperature of 40 ◦ C and then
increased from 50 to 60 ◦ C
Punica Pb2+ 20–50 ◦ C Adsorption capacity increased pH = 5 At 50 ◦ C Endothermic 371.36 [135]
granatum L. from 344.77–371.36 D = 0.5 g/dm3 ΔG◦ (kJ/mol)
Co = 145 mg/ = 27.85
dm3–300 mg/ ΔH◦ (kJ mol/
dm3 L) = 32.28
T = 20–50 ◦ C ΔS◦ (J/mol
K) = 186.16
Black gram Cr(VI) 20–45 ◦ C Removal increased with the rise – At 293 K Endothermic 215.27 – [136]
husk in temperature from 20 to 45 ◦ C ΔG◦ (kJ mol/
L) =
− 11.2830
ΔH◦ (kJ mol/
L) =
− 149.635
ΔS◦ (kJ mol/
K) = 0.417
For example, Owalude and Tella [113] reported rapid percentage Commonly used desorbing agents include organic acids, mineral acids,
removal of hexavalent chromium by modified groundnut hull in the first alkalis/base metallic salts, solvents and complexing agents [149,212].
30 min. This was attributed to the large surface area available for Acid solutions are typically useful for desorbing most of the metallic
adsorption of hexavalent chromium in the first 30 min. However, the ions due to the introduction of H+ ions which decreases the pH and
authors did not notice any significant increase in adsorption capacity protonates the oxygen groups present on the surface of the biosorbent
after 30 min. Process equilibrium was attained in 80 min when all the [213]. The H+ or H3O+ ions will be in competition with the heavy metal
available active sites were saturated by metal ions. In another study by ions present on the active sites of the adsorbent and the acid radical ions
Pei and Liu [118], the authors reported that the adsorption of lead ions form complexes with heavy metals, thereby desorbing the heavy metals.
on grapefruit peel increased with increase in contact time. It was stated A few examples of commonly used acid-based eluents are hydrochloric
that in pectin rich fruits, the time taken to reach equilibrium is rapid acid, nitric acid and sulphuric acid. Some widely used alkali/bases are
[210]. The biosorption in this study was quick, and equilibrium was sodium hydroxide, potassium hydroxide and sodium carbonate [212].
reached in 1.5 h. This was due to larger number of available active sites Complexing agents also effectively remove heavy metals by forming
during the initial stages of biosorption. Jiang et al. [204] also reported stable complexes with the heavy metals on active sites of the adsorbent
similar results when the authors varied the contact time from 5 to 20 min surface [214]. Metallic salts desorb heavy metals through ion exchange
to remove Pb2+ using modified litchi peels. The sorption was seen to process [196,215].
increase from 88% to 93%. The maximum sorption was seen at 120 min. An ideal desorbing agent is one that is cost-effective, environmen
The same conclusion was drawn by Ratan et al. [129] when the authors tally friendly, is easily separable from the biosorbent and has a high
noticed that sorption of nickel ions on modified coconut coir pith affinity towards the biosorbent. The desorption process can be con
increased with the increase in contact time due to the availability of ducted in a batch or column process. Generally, it would be more ideal
active sites for adsorption. Equilibrium was attained at 2 h. Similarly, for the process to take place in a packed column where the eluent is able
Sharma and Bhalerao [209] described that sorption of Cr(VI) on banana to flow through the column [149].
peels increased with increase in contact time. HCl is a commonly used desorbing agent due to its ability to pro
tonate the surface of the biosorbent and facilitate desorption. It has been
5.4. Desorption and reusability of biosorbents used in various studies for desorbing heavy metals from biosorbents
[119,121,138]. For example, Owalude and Tella [113] used 0.01, 0.1,
The two most important deciding factors on the practical applica 1.0 and 1.20 M HCl solution to desorb chromium (VI) adsorbed onto
bility of a biosorbent are its adsorption capacity and its ability to be modified groundnut hull. The authors were able to desorb 68% of
regenerated. From an economic standpoint, the reusability of spent chromium upon contact with 0.3 M HCl. The solution was filtered to
biosorbents is a major criterion for its selection to be used at an indus recover the biosorbent and then heated at 80 ◦ C for 24 h in an oven.
trial scale [211]. Various adsorption-desorption (A-D) studies are listed After biosorbent recovery, it was reused up to at least 3 cycles. Another
in Table 14 along with the desorbing agent used, removal percentage/ desorption study using HCl was conducted by Lasheen et al. [89] in
capacity after desorption and recovery percentage of heavy metals. which the authors investigated the desorption Pb2+ from modified or
The regeneration process involves the separation of the pollutants ange peels. The spent orange peel was treated with 0.2 M HCl to convert
from the biosorbent. After removal, ideally the biosorbent will be able to it into hydrogen form for superior adsorption. Adsorption-desorption
maintain its morphological structure as well as its adsorption efficiency. cycles showed that the removal percentage for Pb2þ was more than
The biosorbent should be used for a number of cycles before being 96% for the first cycle and was between 93.5 and 91.5% in the second-
replaced to reduce cost and reduce further environmental pollution. fourth cycle. The adsorption did not significantly decrease even after
29
Table 13
Optimum contact time for various agriculture waste based biosorbents.
Biosorbent Metals Range Equilibrium time/remarks Experimental Maximum % Reference
removed conditions removal (mg/g) Removal
Coffee waste Pb2þ 0–240 min Te = 30 min T = 25 ◦ C 41.15 – [87]

R: Rapid adsorption occurred within initial 7 mints Co = 10 mg/L
D = 0.010 g
pH = 7.3
Banana peel Cr(VI) Te = 120 min pH = 3 6.1728 96 [85]
Cr(VI) removal increased upto to 1 h and further increase D = 3 g/L
in adsorption time up to 2 h after which there was no T = 25 ◦ C
change
Banana peel Mn2þ 0–120 min Te = 60 min pH = 8 5.7306 94 [90]
T = 25 ◦ C
Litchi peels Pb2+ 1–180 min 120 min pH = 6 78.74 – [92]
D = 0.25 g
Pineapple peel Cd2+ 0–200 min Te = 30 min D = 0.2 g 42.10 – [93]
Pb2+ T = 25 ◦ C 28.55
pH: 4
Co = 100 mg/L
Lemon peel Ni2+ 0–8 h Te = 3 h pH = 5 36.74 – [94]
Uptake increases rapidly within the first hour. Co = 100 mg/L
D = 10 g/L
Banana peel Pb2+ 0–150 min Te = 120 min D = 0.5 g 89.286 – [95]
Cu2+ 5.720
Papaya leaves Pb2+ 0–120 min Te = 15 min pH = 4 284.35 – [96]
Co = 5400 mg/L
D = 0.1 g
Petai peel Pb2+ 0–120 min Te = 15 min pH = 4 36.01 – [96]
Co = 590 mg/L
D = 0.1 g
Papaya peel Cu2+ 0–60 min Te = 45 min D = 0.9 g – 79 [145]
pH = 3
Co = 10 mg/L
Banana peel Cd2+ 5–120 min Te = 60 min pH = 6 27.77 – [97]
Cr3+ D = 0.5 g 38.46
Zn2+ 9.52
Kiwi Cd2+ 5–120 min Te = 60 min pH = 6 15.87 – [97]
Cr3+ D = 0.5 g 41.66
Zn2+ 37.03
Tangerine Cd2+ 5–120 min Te = 60 min pH = 6 17.54 – [97]
Cr3+ D = 0.5 g 47.61
Zn2+ 38.41
Tomato waste Pb2+ 15–75 min Te = 75 min pH = 4 152 – [98]
Rapid biosorption in initial 15 min D = 0.1 g
Pomelo peel Cu2+ 0–180 min Te = 20–40 min T = 30 ◦ C 8 – [161]
Co = 24.86 ppm
D = 0.05 g
Sugarcane As(III) 5–120 min Te = 90 min Co = 0.395 mg/L – 98.9 [139]
bagasse D = 10 g/L
Sugarcane Pb2+ 15–1440 Te = 1440 min pH = 5 52.63 – [104]
bagasse min
Sugarcane Pb2+ 15–1440 Te = 1440 min pH = 5 30.68 – [104]
bagasse min
2+
Sugarcane Pb 15–1440 Te = 1440 min pH = 5 35.09 – [104]
bagasse min
Wheat straw Pb2+ 0–100 min Te = 30 min pH = 4 g/L 50.76 – [35]
Rapid adsorption of metal ions during the first 5 min Co = 100 mg/L
pH = 5.0
Sugarcane As(III) 0–200 min Te = 120 min pH = 7 28.57 – [106]
bagasse As(V) D = 0.3 g 34.48
Sugarcane As(V) 24 h Te = 3 h pH = 4 22.1 – [107]
bagasse T = 22 ◦ C
Sugarcane Co2+ 0–10 h Te = 7 h pH = 6 56.1 – [108]
bagasse Cu2+ 93.5
Ni2+ 93.2
Rice husk Cd2+ 0–200 min Te = 45 min Co = 60 mg/L 45.5 – [110]
Ni2+ D = 0.3 g 55.5
T = 25 ◦ C
Cashew nut Cu2+ 0–60 min Te = 30 min Co = 20–100 mg/L 48.05 – [111]
shell pH = 5.0
D = 2 g/L
T = 30 ◦ C
Groundnut Cr(VI) 0–300 min Te = 80 min pH = 2 131 – [113]
hull T = 30 ◦ C
2+
Garlic peel Pb 1–120 min Te = 40 min 109.05 – [115]
30
Biosorbent Metals Range Equilibrium time/remarks Experimental Maximum % Reference
removed conditions removal (mg/g) Removal
Co = 50 μgm/L
pH = 5
D = 5 mg
Musk melon Pb2+ 0–60 min Te = 10 min D = 0.08 g 167.8 – [116]
peel pH = 5
T = 303 K
Co = 00.1, 0.5, and
1.0 mmol/l
Grapefruit peel Cr(VI) 0–1500 Te = 400 min D=1g 39.0628 – [117]
min
2+
Grapefruit peel Pb 0–700 min Te = 1.5 h – 12.73 – [118]
Grapefruit peel Cd2+ 5–120 min Te = 60 min Co = 50 mg/L 42.09 – [119]
Ni2+ D = 1 g/L 46.13
Cucumber peel Cd2+ 0–200 min Te = 60 min pH = 5 0.998* – [120]
Rapid adsorption in first 15 min
Peanut hull Ni2+ 10–70 min Te = 30 min pH = 6 8.63 – [127]
D = 2 g/L
2+
Coconut pith Ni 0–3 h 2h Co = 50 mg/L 24.39 – [129]
T = 30 ◦ C
pH = 6.0
Tea waste Ni2+ 3h Te = 120 min D = 0.25 g 38.3 – [132]
T = 303 K
Watermelon As(V) 0–25 h Te = 2 h Co = 4 mg/L – 98 [134]
rind As(III) D = 1 g/L – 99
T = 20 ◦ C
Punica Pb2+ 5–120 min Te = 60 min pH = 5.5 371.36 [135]
granatum L. D = 1 g/dm3
T = 20 ◦ C
Black gram Cr(VI) 5–180 min Te = 120 min Co = 100 mg/L 215.27 – [136]
husk T = room temp
Banana stem Hg2+ 0–60 Te = 60 min T = 30 ◦ C 132.25 – [138]
Rapid increase from 0 to 10 min
*
Unit: mmol/g.
four cycles. In a study conducted by Villen-Guzman et al. [94], the During the second adsorption cycle after the desorption, results showed
removal efficiency of Ni2+ from modified lemon peel remained high, up a significant decrease in the adsorption. The removal efficiency was
to 90% even after 5 adsorption-desorption cycle using HNO3 and H2SO4 27.4% for 0.1 N HCl and 30.2% for 0.5 N HNO3. The decrease in the
as the desorbing agents. Guo et al. [33] also used 0.1 M HCl to recover removal efficiency was attributed to structural changes caused due to
Cu2+, Cd2+, Pb2, Zn2+and Ni2+ from modified orange peel. Even after 10 acid treatments for desorption. Desorption treatments can often damage
adsorption-desorption cycles, the removal efficiency remained high for the structure and morphology of the adsorbent. Therefore, the desorbing
Cu2+, Cd2+ and Pb2+ at 97%, 90% and 99% respectively. However, agents and concentrations need to be chosen carefully in order to ach
Zn2+and Ni2+ showed a significant decrease of 78% and 75%, respec ieve high recovery of heavy metal and maintain the structure of the
tively after 10 cycles. This may be due to the saturation of active sites on adsorbent.
the adsorbent surface. Similarly, Liu et al. [102] used 0.01 M HCl to
desorb Cd2+ and Pb2+ ions from modified sugarcane bagasse. When the 6. Column studies
3 cycles of adsorption-desorption of modified and unmodified sugarcane
bagasse were compared, the modified sugarcane bagasse shows higher Most of the adsorption studies conducted for the removal of heavy
removal rates. The removal rate of Cd2+ was 31.9% higher for modified metals in the past few decades evaluate the process in a batch system.
sugarcane bagasse and 43% higher for Pb2+. The citric acid and Fe3O4 However, the adsorption process on an industrial scale generally takes
aided in the strengthening of the biosorbent as well as creating more place in a continuous system. Some types of reactors used are continuous
active sites for adsorption. In various studies, the authors used multiple fluidize bed and pulsed bed, continuous moving bed, continuous fixed
desorbing agents to find out the optimum one. For example, Abbaszadeh bed reactors (upflow or downflow). Among the types of reactors, fixed
et al. [207] used desorbing agents such as H2SO4, HNO3 and HCl to find bed column configuration is preferred for heavy metal removal [216]. It
the most suitable desorbing agent for desorbing lead ions from is necessary to evaluate the performance of the adsorbent in a contin
magnetically modified papaya peel waste. It was found that maximum uous flow system. A list of studies using agriculture based biosorbents,
desorption of Pb2+ ions was achieved after shaking for 2 min. HCl (0.1 conducted in continuous systems including column properties have been
mol/L) with a volume of 3 ml yielded the best desorption. The adsorbent listed in Table 15. Various mathematical models have been used to
was further washed using HCl (0.1 mol/L) and deionized water to test evaluate the efficiency and applicability of the columns in an industrial
reusability. The adsorbent could be reused for up to 10 cycles with a scale operation. These mathematical models are based on assumption of
reusability efficiency greater than 84%. Ahmad et al. [195] also carried axial dispersion, external mass transfer, intraparticle diffusion and
out desorption studies using HCl (0.1 M), H2SO4 (0.1 M) and HNO3 (0.1 nonlinear isotherms. Some of these models include Thomas, bed depth
M) to desorb Pb2+ and Cd2+ ions from chemically oxidized pineapple service time (BDST), the Adams and Bohart model, Yoon–Nelson, Clark,
peel. Similar to the results obtained by Abbaszadeh et al. [207], HCl (0.1 Wolborska and modified dose–response model and it is noteworthy that
M) was the most efficient and desorbed 90% of Cd2þ and 87% of Pb2þ. the Thomas model is widely used for column studies [216]. This model is
Another comparative study to find the best desorbing agent was con based on the assumption that the adsorption process follows the Lang
ducted by Kucukcongar et al. [127] where the authors used 0.1 N HCl muir isotherm model with no axial dispersion. Details of this process are
and 0.5 N HNO3 to recover Ni2+ ions from magnetic peanut hull waste. depicted in Fig. 5.
31
Table 14
Adsorption-desorption studies for various agriculture based adsorbents.
Biosorbent Metals Maximum Heavy metal removal percentage after % Recovery of heavy Desorbing agent Cycles Reference
removed removal (mg/ A-D cycle metal
g)
Orange peel Pb2+ 476.1 – 1st 2nd 3rd cycle (Pb2+) 0.05 M HCl 3 [88]
Cd2+ 293.3 = 96.7, 96.5, 95%
Ni2+ 162.6 1st 2nd 3rd cycle (Cd2+)
= 97.2, 95.6, 93.7%
1st 2nd 3rd cycle (Ni2+)
= 95.8, 95.4, 90.8%
Orange peel Pb2+ 73.53 1st A-D cycle = 96% – 0.2 M HCl 4 [89]
2nd–4th cycle = 93.5–91.5
2+ 2+
Pineapple peel Cd 42.10 – Cd 0.1 M HCl – [93]
Pb2+ 28.55 0.1 M HCl = 90% 0.1 M H2SO4
0.1 M H2SO4 = 86% 0.1 M HNO3
0.1 M HNO3 = 88%
Pb2+
0.1 M HCl = 87%
0.1 M H2SO4 = 83%
0.1 M HNO3 84%
Lemon peel Ni2+ 36.74 – 90% 0.1 M HNO3 5 [94]
90% 0.1 MH2SO4
Tomato waste Pb2+ 152 – 8.188% 0.1 M Ammonium – [98]
0% acetate
53.473% Water
94.247% 0.1 M HCl
0.1 M sodium
EDTA
Sugarcane bagasse Cd2+ 33.2 After 3 cycles the removal rate for Cd2+ 0.01 M HCl 3 [102]
Pb2+ 116.7 and Pb2+ were 48.2% and 82.6%
Sugarcane bagasse (citric Pb2+ 52.63 – 96.8% 0.1 M HCl – [104]
acid modified)
2+
Sugarcane bagasse Pb 30.68 – 62.9% 0.1 M HCl – [104]
(sodium hydroxide
modified)
Sugarcane bagasse(citric Pb2+ 35.09 – 67.7% 0.1 M HCl – [104]
acid and sodium
hydroxide modified)
Sugarcane bagasse As(III) 28.57 At the end of 5th cycle the adsorption – 0.01 M HCl 5 [106]
As(V) 34.48 efficiency of As(III) was reduced by
14% and As(V) was reduced by 22%
Sugarcane bagasse As(V) 22.1 – 17% 30% HCl – [107]
85% 1 M NaOH
Rice husk Cd2+ 137.16 At the end of the 4th cycle the removal – 0.5 M HNO3 4 [70]
percentage was 75%
Groundnut hull Cr (VI) 131 – 79.62% was the highest 0.01 M HCl 3 [113]
desorption efficiency for 0.1 M HCl
0.3 M HCl 0.3 M HCl
1 M HCl
1.20 M HCl
Cucumber peel Cd2+ 0.998* – 97% 100 mmol HCl 5 [120]
Orange peel Cu2+ 59.77 97% – 0.1 M HCl <10 [33]
Orange peel Cd2+ 125.63 90% – 0.1 M HCl <10 [33]
Orange peel Pb2+ 141.84 99% – 0.1 M HCl <10 [33]
Orange peel Zn2+ 45.29 78% – 0.1 M HCl <10 [33]
Orange peel Ni2+ 49.14 75% – 0.1 M HCl <10 [33]
Peanut hull Ni2+ 8.63 0.1 N HCl = 27.4% 0.5 N HNO3 = 88.3% 0.1 N HCl 2 [127]
30.2% 84.8% 0.5 N HNO3
A significant decrease was observed in
the second A-D cycle.
Banana peel Pb2+ 90 – 70.64% 0.1 M HCl 2 [30]
Tea waste Pb2+ 153 Pb2+ and Cd2+ – 0.1 M HCl 5 [131]
Cd2+ 222 1st A-D cycle = 67.3% and 77.9%
5th A-D cycle (Pb2+) = 55%
5th A-D cycle (Cu2+) = 51.8%
Watermelon rind As(V) 98% – As(V) 0.1 M NaOH 4 [134]
As(III) 995 1st A-D cycle = 98%
2nd 3rd and 4th A-D
cycle = 47%, 15%, 50%
As(III)
1st A-D cycle = 93%
2nd 3rd and 4th A-D
cycle = 32%, 11%, 20%
Banana stem Hg2+ 132.25 – 0.1 M HCl showed 0.1, 0.01, 0.001, – [138]
highest desorption and 0.0001 M HCL
98.5%
*
Unit: mmol/g.
32
Table 15
Column studies for various agricultural waste-based adsorbents.
Adsorbent Heavy Bed Column Adsorbent Internal Inlet Volumetric Adsorption Reference
metal height height dose/mass diameter concentration flow rate capacity
Spent grains Cr(III) – 39 cm 25 g 3.2 cm 50 mg/L 1.5 ± 0.1 mL/ 16.7 mg/g [222]
min
Sesame waste Cd(II) 2 cm – 124 g 2.2 cm 60 mg/L 2.5 mL/min 22.88 mg g [220]
Sulphured orange peel Pb2+ – – 100 mg 8 mm 10 mg/L 7.2 mL/h 164 mg/g [91]
Zn2+ 100 mg/L 80 mg/g
Phosphoric acid modified Pb2+ – 20 cm 0.5 g 1 cm 0.5 mmol/L 6.25 mL/min 73.7 mg/g [223]
sugarcane bagasse
Grapefruit modified with Cr(VI) – 1.5 m 75 g 0.3 m 35 mg/L 0.5–2.5 L/min 39.0628 mg/g [117]
H2O2
Strychnos nux vomica fruit Cr(VI) 3–7 cm 15 cm – 1.5 cm 50 mg/L 5 mL/min 32.52 mg/g [221]
shell
Date palm trunk fiber Cd(II) – 50 m 4g 1.1 cm 110 mg/L 10 mL/min 20.93 mg/g [224]
Rapeseed biomass Pb2+ 6 cm 15 cm 0.7 g 1.5 50 mg/L 2.5 mL/min 20.37 mg/g at 50 [225]
100 mg/L mg/L
40.04 mg/g at
100 mg/L
Orange peel Pb2+ – – – 8 mm 10 mg/L 6.1 mL/h 209.8 mg/g [32]
Zn2+ 100 mg/L 56.18 mg/g
Fig. 5. Overview of column studies evaluation.

(Adapted from [217]).
Column studies are based on breakthrough curves. These curves are a (II) uptake capacity had reduced. At a bed height of 2 cm, an optimum
graphical plot of contaminant-effluent versus time. Factors such as bed breakthrough curve was achieved. The authors also varied the flow rate
height, flowrate and amount of adsorbent in the column also greatly from 2.5 to 4.5 mL/min. The results showed that as the flow rate
affect the adsorption capacity [218,219]. For instance, in a study con increased from 2.5 and 4.5 mL/min, the uptake capacity of Cd(II)
ducted by Cheraghi et al. [220], the authors used sesame waste biomass reduced from 22.88 to 15.13 mg/g. Moreover, by fitting the experi
for the removal of Cd(II) from aqueous solutions in a fixed-bed column. mental data into mathematical models, the Yoon–Nelson and Thomas
The authors reported that with the increase in bed depth from 2, 4 and 6 models were able predict the adsorption performance for Cd(II)
cm, there was an increase in removal efficiency to 67.67, 75.88, and adsorption in a fixed-bed column. Rosales et al. [117], also evaluated the
77% respectively. This can be attributed to increase in biosorbent mass effect of flow rate on the adsorption of Cr(VI) on grapefruit peelings
in the column and thereby the adsorbent total mass surface area avail based on the Homogeneous Surface Diffusion Model (HSDM) with an
able for adsorption which would provide more adsorption sites. On the adsorption column of height 1.5 m, volume 100 L and internal diameter
other hand, it was observed that with the increase in bed depth, the Cd 0.3 m. The results explained that upon increasing the flow rate, the
33
breakthrough time was obtained earlier and the biosorbent was satu 8. Cost analysis
rated in a shorter amount of time. At an effluent concentration of 90% of
the initial value, the biosorbent would be exhausted in 62.5, 44, 34.5, Cost analysis is a very essential factor to evaluate the practical
29 days for Cr(VI) with flow rates of 0.5, 1, 1.5, 2, 2.5 L/min. Nakkeeran applicability of the adsorption process. In general, it is often mentioned
et al. [221] also noticed the similar trend when the authors studied the that agricultural wastes are very cost effective in comparison to com
effect on adsorption by varying flow rates of the Cr(VI) laden influent on mercial adsorbents. This section aims to compile some of the scattered
Strychnos nux vomica fruit shell. It was reported that the breakthrough information regarding the costs of biosorbents. The cost analysis studies
time had declined as flow rate increased. The biosorption capacity had are listed in Table 17. In a study conducted by Sharma and Ayub [231],
also reduced as the flow rate increased. Moreover, the removal per the authors conducted a thorough cost analysis of using pea (Pisum
centage of Cr(VI) reduced from 65.14% to 34.69% with an increase in sativum) pod peels, tea (Camellia sinensis) & ginger (Zingiber officinale)
flow rate. Upon evaluation of mathematical models, the Thomas and mix and banana (Musa lacatan) peels used to adsorb Cr(VI) from
BDST model presented better agreement with the equilibrium data. The wastewater. According to their analysis, the cost to adsorb 1 g of Cr(VI)
effect of initial metal concentration was also evaluated at a fixed bed from wastewater was Rs. 9.14, Rs. 4.71, and Rs. 3.11 respectively. The
height of 3 cm and a constant flow rate of 5 mL/min. The results cost is significantly cheaper when compared to adsorption by commer
revealed a decrease in breakthrough time with an increase in initial cial activated carbon which was Rs. 142.145. Peanut hull is a very
metal concentration. The biosorption capacity had increased with the commonly used agricultural waste that is employed in biosorption
increase in initial metal concentration [221]. This can be attributed to processes. In a study conducted by Ali et al. [203], the author stated that
the presence of Cr(VI) molecules on the film layer formed on the surface. the Egyptian peanut hulls that have been used to remove Cu(II) in their
This will initiate a rapid movement at higher concentration of metal to study were inexpensive and cost L.E. 800/t. The finished product
the biosorbent surface because of elevation in the coefficient of mass including all costs such as peanut hulls, electrical energy, handling,
transfer. The removal percentage had reduced from 65.14% to 37.24% transportation, chemicals, drying, etc. was approximately L.E. 2000/t.
with the increase in metal ion concentration. Like many studies, higher Another common and abundantly available agricultural waste is rice
removal of chromium occurred at low flow rates, low initial metal ion husk. It was reported that the cost of using chemically activated risk
concentration and larger bed height. husk as an adsorbent was 2.579 USD which is very economical. This cost
covers collection of the rice husk, cleaning costs, size reduction costs,
7. Biosorption of heavy metals from real industrial wastewater drying and pyrolysis costs, and chemical activation costs. Since the
agricultural waste was collected by farmers in this study, it was free of
Industrial wastewater consists of various types and quantities of cost [232]. Moreover, during mass production these costs are expected
pollutants depending upon the industry they are discharged from. Ef to drop further. Elhafez et al. [233] also performed a techno-economic
fluents from industrial wastewater usually consists of different types of analysis on the usage of rice husk based biosorbent. Rice husk as a
ions that can compete with the heavy metal ions for active sites on the raw material can be sold at a low price of 42 €/t, for a 1200 t/y pro
surface of the biosorbent. Therefore, it is necessary to analyse the bio duction rate. The operational cost was estimated to be 50,400 €/y. The
sorption process using real industrial wastewater as most of the studies authors estimated that rice husk-based adsorbent would cost 420 €/t. On
use synthetic heavy metal wastewater. For example, Razak et al. [226] the basis of an adsorbent of 1200 tons/year, it was estimated that the
used phosphoric acid to modify kenaf fiber for the removal of copper(II) revenue of the plant would be higher than the operational costs, leaving
ions from electroplating and wood treatment industry. The adsorption a net profit of 144,000 €/y. More details on the cost calculations are
capacity of copper ions from the electroplating industry and from the listed in Table 17. Sugarcane bagasse is another effective and common
wood treatment industry was 33.55 mg/g and 37.18 mg/g, respectively. agricultural waste used in the adsorption of heavy metals. In a study
In a single metal ion synthetically spiked system, the adsorption capacity conducted by Gupta et al. [234], it was reported that the total cost for
was 57.14 mg/g. Electroplating industry contains various other metal the preparing 1 kg of adsorbent was estimated as INR 49.28, INR 309.65
ions as copper, zinc, tin and gold whereas wood treatment effluent is rich and INR 103.40 for sugarcane bagasse, acid activated sugarcane bagasse
in arsenate. Therefore, more than one type of ions was competing for the and base activated sugarcane bagasse, respectively. Chemical modifi
active sites on the biosorbent and reduced the adsorption capacity. In cation raises the price of the adsorbent material. In this study, the un
another study, Abdolali et al. [227] used a mixture of tea waste (TW), modified sugarcane per gram of Cu(II) removal cost INR 10.18. The cost
maple, leaves (ML) and mandarin peel (MP) to remove Cd, Cu, Pb and Zn to remove of 1 g of Cu(II) from the wastewater using acid activated
from real and synthetic wastewater. The real wastewater was taken from sugarcane bagasse and base activated sugarcane bagasse was INR 57.88
the primary effluent, downstream of the Malabar WWTP sedimentation and INR 50.19, respectively. Although the chemical modification
tanks collected from Sydney WaterPlant, NSW, Australia. The experi increased the price, it was still found to be significantly cheaper than the
ment was carried out in a packed bed column. Prior to the adsorption commercial activated carbon purchased by the authors which costed
experiment, the sewage was settled for 24 h and filtered using a 150 μm INR 649.47. Bhatnagar et al. [86], reported that lemon peels were an
sieve. The wastewater was spiked with heavy metal (20 mg/L) solution efficient an economic option for the removal of heavy metals from waste
due to undetectable amounts in municipal wastewater. The pH was not water. The cost of lemon peels was approximated to 5–6 USD/100–200
altered. The wastewater consisted of various other contaminants tonnes whereas the cost of activated carbon was estimated to 2000 USD/
mentioned in Table 16. The results showed that the biosorbent removed tonne. The total cost of the final adsorbent including costs of electrical
more than 90% of Cd(II), Cu(II), Pb(II) and Zn(II) ions from 3227, 2617, energy, transportation, chemicals was estimated to 100–200 USD/ tonne
1714 and 2019 mL municipal wastewater in 322, 261, 171 and 201 min, which is about 10 times cheaper than the activated carbon. Fawzy et al.
respectively. It was also reported that the biosorption capacity was [235] performed a techno-economic analysis on adsorption of cadmium
similar to that achieved with synthetic wastewater. Bulgariu et al. [228] ions by olive leaves (Olea europaea L.) waste. It was assumed that annual
used sulphur based-soy waste for removal of Pb(II), Cu(II) and Ni(II) feed of industrial wastewater which is 7000 m3/year was being treated
from industrial water from a local printing circuit board company. In the with adsorption as the tertiary stage of the wastewater treatment plant.
wastewater samples, the concentration of heavy metal ions was adjusted As shown in Table 17, the net cost which is BC (benefit cost)–OC
to 0.4 mmol/M(II)L. It was reported that 98% of the heavy metals were (operating cost) for the application of adsorption as tertiary treatment
removed from the water and achieved the permissible limit. The values was 0.014 USD/m3. The positive value depicts that the adsorption sys
of Pb(II), Cu(II) and Ni(II) had reduced from 83.70 mg/L, 25.50 mg/L, tem would eventually gain financial profits and compensate for the AC
23.50 mg/L to 0.4381 mg/L, 0.1673 mg/L, 0.6237 mg/L after (amortization cost). The payback period was calculated as AC (0.0080
biosorption. USD/m3)/the annual net profit (0.0014 USD/m3/year) which was 5.7
34
Table 16
Removal of heavy metals from industrial wastewaters.
Biosorbent Heavy Type of wastewater Contaminants/wastewater properties Adsorption capacity(AC)/ Reference
metal removal %/concentration after
biosorption (C)
Sulphur-based soy waste Pb(II) Printing circuit board company Pb(II) = 83.70 mg/L C = 0.4318 mg/LC = 0.1673 [228]
Cu(II) Cu(II) = 25.50 mg/L mg/LC = 0.6237
Ni(II) Ni(II) = 23.50 mg/L mg/L
NH4 = 25.89 mg/L
Nitrate = 25.89 mg/L
Sulphides = 0.87 mg/L
Chloride = 182. 16 mg/L
COD = 258.16 mg O2/L
Water hardness = 17.21◦ Ge
Kenaf modified by Cu2+ Electroplating industry (EP) and wood Cu2+ (EP) = 218.3 mg/L Cu2+ AC (EP) = 37.18 mg/g [226]
phosphoric acid treatment industrial effluent (WT) Cu2+ (WT) = 300.1 mg/L Cu2+ AC (WT) = 35.55 mg/g
% Removal Cu2+ (EP) = 88.2%
Cu2+ (WT) = 61.5%
Cajanus cajan husk Cu(II) Electroplating industry pH = 2.6 AC = 16.4348 mg/gAC = [229]
modified with NaOH Zn(II) COD = 675 mg O2/L 6.1643 mg/g
BOD = 292 mg O2/L
Cu(II) = 313.6 ppm
Zn(II) = 248.4 ppm
Pb(II) = 18.2 ppm
Total suspended solids = 445 ppm
Tea waste (TW), maple Cd(II) Primary effluent, downstream of the Malabar pH = 7.37 ± 0.1, salinity = 0.45‰, % Removal of all heavy metals [227]
leaves (ML) and Cu(II) WWTP sedimentation tanks from Sydney turbidity = 83.5 NTU, Electrical was more than 90%
mandarin peel (MP) Pb(II) Water treatment plant in Sydney, Australia conductivity = 863 μS/cm
Zn(II) Total dissolved solids = 567 mg/L
Total suspended solids = 97 mg/L
Ammonium = 62 mg/L Nitrate =
3.45 mg/L, Orthophosphate = 5.4
mg/L
Total organic carbon = 21.55 mg/L
Chemical oxygen demand (COD) =
246 mg/L
Chloride = 118.32 mg/L
Calcium = 28.62 mg/L Magnesium =
9.67 mg/L
Iron = 0.29 mg/L
Copper = 0.2 mg/L
Lead = 0.35 mg/L Manganese = 0.05
mg/L
Nickel = 0.03 mg/L
Sugar beet pulp Zn2+ Galvanization (GI) industry and an abandoned Zn2+ (GI) = 420 mg/L At pH = 5 [230]
Cu2+ sulphide mine (SM) Cr2+ (GI) = 10.8 mg/L Zn2+ AC (SM) = 2.3 mg/g
Fe2+ (GI) = 22.9 mg/L Cu2+ AC (SM) = 1.3 mg/g
Cu2+ (SM) = 15.9 mg/L Zn2+ AC (GI) = 20.4 mg/g
Zn2+ (SM) = 22.4 mg/L
Fe2+ (SM) = 87.1 mg/L
pH (GI) = 2
pH (SM) = 2.3
Banana stem modified Hg2+ Chlor-alkali industry situated pH = 8.82 % Removal = 100 [138]
with formaldehyde Turbidity = 36.12 NTU
Conductivity (ms/cm) = 21.14
Hg(II) = 17.60 mg/L
Pb(II) = 2.18 mg/L
Cd(II) = 1.12 mg/L
Mg(II) = 33.17 mg/L
Ca(II) = 51.14 mg/L
Na(I) = 241.56 mg/L
PO43− = 19.14 mg/L
NO3− = 21.17 mg/L
NH4+ = 31.54 mg/L
Cl− = 517.64 mg/L
BOD = 79.55 mg/L
COD (mg O2/L) = 214.86 mg/L
Rapeseed biomass Pb2+ Factory wastewater in Romania pH = 7.78 0.27 mg/g [225]
TSS (mg/L) = 69 % Removal = 94.47
COD (mg/L) = 515.65
Pb2+ (mg/L) = 4.88
Cl− (mg/L) = 150
Total hardness (◦ G) = 12.4
35
Table 17 Table 17 (continued )

Cost of some agriculture wastes based adsorbents. Material Heavy Costs References
Material Heavy Costs References metal
metal
USD/m3/y
Peanut hull Cu(II) Egyptian peanut hulls = L.E. [203] Costbiosorbent = − 0.409 × 10− 3
800/t USD/m3/y
Finished products (peanut Costenergy = − 1.477 × 10− 3
hulls, electrical energy, USD/m3/y
handling, transportation, Costmaintenance = − 0.016 ×
chemicals, drying, etc.) = L.E. 1010− 3 USD/m3/y
2000/t Benefit-cost (BC) =
Pea pod peels Cr(VI) Rs. 9.14/1 g removal of Cr (VI) [231] 4.432×10− 3 USD/m3/y
Tea (Camellia Rs. 4.71/1 g removal of Cr (VI) Net profit = 1.421 × 10− 3
sinensis) & ginger Rs. 3.11/1 g removal of Cr (VI) USD/m3/y
mix Payback period = 5.75 years
Banana Water caltrop shell Cr(VI) Water caltrop shell = free of [238]
Sugarcane bagasse Cu(II) INR 49.28 for preparation of 1 [234] charge
Physically activated kg sugarcane bagasse Cost for Cr(VI) removal
Sugarcane bagasse INR 309.65 for preparation of (expense of chemical and
Chemically 1 kg of physically activated electrical energy for
activated sugarcane sugarcane bagasse preparation of biosorbent) =
bagasse INR 103.40 for preparation of USD 93.39/ton
1 kg of chemically activated Pineapple and Bamboo Ni (II) Costs on the basis of 10 kg: [239]
sugarcane bagasse sugarcane Stem Based Electricity = Rs. 1280.44
bagasse Adsorbents (BSAC) Nitrogen gas = Rs. 548.7
Lemon peel Cobalt Lemon peels = ≈USD 5–7/ [86] Phosphoric acid = Rs. 2100
tonnes Bamboo stem = Rs. 320
Final product (chemicals, Total = Rs. 4249.1
electrical energy, etc.) = ≈USD Miscellaneous operating costs
100–200/tonnes (2%) = Rs. 90.981
Rice husk Cu(II) Initial capacity of rice husk [233] Grand total = Rs. 4340.082
(RH) production = 1200 tons/ BSAC cost (per gram) = 0.0072
year $/g
Plant operation for RH Walnut shell Pb2+ Cost of treating 1 L of [236]
treatment specification = Cd2+ wastewater = Rs. 1.3
operate for 8-h shifts per day Sulphur-based soy Pb(II) Cost 6.56 kg of soy waste [228]
(7 days per week, 48 weeks per waste biomass Cu(II) biomass = − 0.11 €
year (5 weeks for Ni(II) Cost of 1.31 L of sulphur based
maintenance); total production chelating agent = 6.7 €
days, 336 days per year Total cost = 6.16 € (to remove
Rice husk = 420€/t 0.5 mmol Pb(II)/L)
Establishment capital (EC) =
436,800€
Energy cost for mill power and years. This duration was shorter than 10 years which was the lifetime of
power balance = 32,040 €/y the implying the practicality of the investment.
Labour cost = 5 workers, 670
€/month, 14 months: 46,900
€/y 9. Conclusion, future prospects and recommendations
Admin costs = 1 director, 1500
€/month, 14 months; 1 To address the concern of heavy metal removal, adsorption process
chemist/R&D consultant, 1200 has various advantages such as ease of operability, low-sludge produc
€/month, 14 months; and 3
admin staff, 1200 (average)
tion, removal of heavy metals presents at a low concentration when
€/month, 14 months compared to other commonly used technologies such as membrane
Break-even point for technology, ion exchange, coagulation/flocculation etc. Biosorbents
production of the adsorbent modified chemically via acids, alkalis, polymers, grafting co-
materials = 500 t/y (when
polymerization and with metal salts to produce magnetic biosorbents
production reaches 3200 t/y, a
much higher return on and modifying with other organic chemicals have proven to be a cost-
investment of 62% is estimated effective and highly efficient. Chemical modification with acids often
and the net profit of 420,000 showed the highest sorption efficiency. It can be concluded that most of
euros) the biosorption processes follow the Langmuir or Freundlich isotherm
Pine bark Fe2+ Cost of pine bark adsorbent = € [240]
Mn2+ 55.00/m3
model. More commonly, pseudo-second-order kinetic model is appli
Carrot, tomato and Co (II) PET bottles and tomato and [237] cable to the biosorption process. The process is usually spontaneous and
polyethylene carrot waste = free of cost endothermic in nature. The regeneration of biosorbents was most
terephthalate waste Adsorbent price including effective when acids were used as eluents which allowed some bio
power consumption and
sorbents to be reused efficiently up to 10 times. The cost analysis
chemicals used = 58.93 USD/
kg of adsorbent produced revealed that agricultural waste-based biosorbents are significantly
Olive leaves Cd2+ Economic estimation and [235] cheaper than commercial biosorbents such as activated carbon. How
payback period of adsorption ever, there are many key areas of biosorption that need to be addressed
lifetime of 10 years (tertiary in order to bring lab scale studies to large-scale applications in the
treatment):
Initial amortization cost (AC) =
industry.
8.164 × 10− 3 USD/m3
Costchemical = − 1.108×10 • Most of the studies are based upon mono-metal, synthetically pre
pared heavy metal solutions. Real wastewater needs to be used in the
36
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Journal of Water Process Engineering 46 (2022) 102446

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Journal of Water Process Engineering

Biosorption of heavy metals from aqueous solution by various chemically

1. Introduction environment [4]. Industrial wastewater consists of various types of

Various types of adsorbent materials including natural, biological and Table 1

2.1.3. Electrodialysis 3. Biosorption

Coffee waste Pb2+ 41.15 – T = 25 ◦ C 0.991 Langmuir [87]

Table 5 Table 5 (continued )

Fig. 2. Some examples of modifying agents used in chemically modifying biosorbents.

Ion exchange, electrostatic

Pineapple Waste Pb2+ – 85.88 NaOH [179]

Co2þ 56.1 Co = 0.79 mmol/L

Coffee waste Pb2þ 0–0.030 g 10 mg Co = 10 and 100 mg/L 41.15 [87]

Coffee waste Pb2þ 0–100 mg/L 25 mg/L D = 0.010 mg 41.15 – [87]

Coffee waste Pb2þ 0–240 min Te = 30 min T = 25 ◦ C 41.15 – [87]

Fig. 5. Overview of column studies evaluation.

Table 17 Table 17 (continued )

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