Arab Journal of Basic and Applied Sciences

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Removal of heavy metals from aqueous media by

biosorption

Ali Ali Redha

To cite this article: Ali Ali Redha (2020) Removal of heavy metals from aqueous
media by biosorption, Arab Journal of Basic and Applied Sciences, 27:1, 183-193, DOI:
10.1080/25765299.2020.1756177

To link to this article: https://doi.org/10.1080/25765299.2020.1756177

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ARAB JOURNAL OF BASIC AND APPLIED SCIENCES University of Bahrain
2020, VOL. 27, NO. 01, 183–193
https://doi.org/10.1080/25765299.2020.1756177

REVIEW ARTICLE

Removal of heavy metals from aqueous media by biosorption

Ali Ali Redha
Department of Chemistry, College of Science, University of Bahrain, Kingdom of Bahrain

ABSTRACT ARTICLE HISTORY

In this literature review, the removal of heavy metals from aqueous media by an environ- Received 27 September 2019
mentally friendly method, known as biosorption has been discussed. Biosorption can be Revised 28 March 2020
referred to as an alternative to the common unsustainable industrial methods currently Accepted 31 March 2020
used. Removal of heavy metals from aqueous media by biosorption can take place by the
KEYWORDS
aid of different types of biomass including algae, fungi, bacteria and plants. The mecha- Biosorbents; biosorption;
nism(s) of biosorption can vary accordingly, mechanisms include physical adsorption, ion biosorption mechanisms;
exchange, complexation, precipitation and transport across the cells. The efficiency of removal of heavy metals
removal of heavy metals by a specific biosorbent at specified conditions can be compared
by the calculated biosorption capacity of the respected biosorbent. Several factors can influ-
ence the biosorption capacity of different biosorbents, that mainly includes water pH, tem-
perature, contact time, biomass dosage and initial heavy metal concentration. This literature
review focuses on the types of biosorbents, mechanisms of biosorption and factors affecting
biosorption capacity. In addition, biosorption, as a method which has the potential of com-
peting with common industrial methods has been critically analysed.

1. Introduction not appropriate for removal of heavy metals at low

With the growth of the industrial world, environmen-
tal challenges have also increased. A common type
of pollution the world is currently struggling with is
water pollution. Water pollution can be due to many
different causes such as agriculture, sewage and
wastewater, oil pollution and radioactive substances.
Wastewater, especially which is discarded by indus-
tries, can contain a wide range of heavy metals.
Heavy metals are considered as one of the common
causes of water contaminates. Heavy metals are non-
degradable and accumulate in the environment.
Heavy metals in streams, lakes and seas contaminate
water in which marine organisms live, for example
fish which is consumed by humans, not only the
aquatic life becomes threated, but the human health
also becomes in danger as those heavy metals bio-
accumulate through the food chain. The major water
contaminants are arsenic, cadmium, chromium, cop-
per, lead, nickel and zinc (Jaishankar, Tseten,
Anbalagan, Mathew, & Beeregowda, 2014).
Heavy metals are removed from industrial waste-
water by conventional methods such as reverse
osmosis, electrodialysis, ultrafiltration, industrial ion
exchange process and chemical precipitation (Sao,
2014). These common industrial methods of heavy
metal removal have several disadvantages such as
being expensive, requiring high amounts of energy,
concentrations (1-50 mg/L), requirement of high
amounts of reagents, causing secondary pollution
through the production of chemical sludge and dis-
posal of floc residues making these methods non-
sustainable in the long run (Wei et al., 2016). An
alternative environmentally favourable method of
heavy metal removal can be through biosorption
methods. Biosorption methods are considered sus-
tainable and more efficient in removal of heavy met-
als from aqueous media.
In this literature review, biosorption process will
be discussed with an evaluation of different types of
biosorbents, the mechanisms involved in biosorption
and factors affecting the biosorption capacity of
biosorbents.
2.1. Biosorption – a deeper insight
Biosorption is a biological physico-chemical process
in which a biological material, such as plant biomass
or microorganisms, is used to absorb or adsorb a tar-
get species, such as metal ions or dyes (Gadd, 2009).
In a biosorption process, two phases are present, a
solid phase which it is referred as the biosorbent
(e.g., plants, bacteria and fungi) and a liquid phase
which is usually aqueous and contains the metal
ions which are known as the sorbate (Abbas Ali,

CONTACT Ali Ali Redha ali96chem@gmail.com Department of Chemistry, College of Science, University of Bahrain, Kingdom of Bahrain
ß 2020 The Author(s). Published by Informa UK Limited, trading as Taylor & Francis Group on behalf of the University of Bahrain.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/), which permits
unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
184 A. ALI REDHA
Mohamed Sihabudeen, & Zahir Hussain, 2016). Algae,
bacteria, fungi and plants are the most common bio-
sorbents used for the removal of heavy metals from
aqueous media. The main biosorption site of the bio-
logical sorbents is their cell wall (Tsezos,
Remoundaki, & Hatzikioseyian, 2014). The cell walls
of different biosorbents contain a range of different
functional groups that contribute in biosorption pro-
cess, the possible functional groups which are cap-
able of biosorbing heavy metals are hydroxyl (found
in alcohols and carbohydrates), carboxyl (found in
fatty acids, proteins and organic acids), amino (found
in proteins and nucleic acids), ester (found in lipids),
sulfhydryl (found in cysteine (amino acid) and pro-
teins), carbonyl (can be terminal such as in alde-
hydes and polysaccharides, or internal such as in
ketones and polysaccharides too) and phosphate
groups (found in DNA, RNA and tissue plasminogen
activator) (Javanbakht, Alavi, & Zilouei, 2014). The
functional groups of a biosorbent contributing in the
removal of a specific metal can be studied and ana-
lysed using several analytical methods such as titra-
tion, infrared spectroscopy (IR), raman spectroscopy,
X-ray photoelectron spectroscopy (XPS), energy-dis-
persive X-ray spectroscopy (EDS) and X-ray absorp-
tion fine structure spectroscopy (Javanbakht
et al., 2014).
The potential of biosorption of a metal ion by a
biosorbent is evaluated by the biosorption capacity
value and equilibrium time for the biosorption pro-
cess. Biosorption capacity is calculated according to
the following formula:
qe ¼ ðC0 Ce Þ V=W
where qe is the biosorption capacity (in mg of
metal/g of biosorbent), C0 and Ce are the initial and
equilibrium concentration of metal ion solution (in
mg/L) respectively, V is the volume of metal ion
solution (in L), and W is the amount of biosorbent
material dose used (in g) (Wei et al., 2016). The
higher the biosorption capacity, the higher the
amount of heavy metal ion(s) a biosorbent can bio-
sorb. Under optimum pH of media and temperature,
the maximum biosorption capacity can be achieved.
Optimising factors such as contact time of biosorb-
ent and metal ion solution, and the dosage of bio-
sorbent can further enhance the biosorption
capacity, nevertheless pH and temperature are the
main influential factors. While choosing a biosorbent
for the removal of a specific metal ion, it is highly
significant to consider the biosorption capacity. It is
recommended to use biosorbents with higher bio-
sorption capacities, as this would suggest that higher
amount of sorbate can be biosorbed, biosorbents
with low biosorption capacity will ultimately require
their replacement. However, other aspects should be
also considered while choosing the biosorbent, such
as the degree of sustainability with respect to any
undesirable effects of using the biosorbent on the
environment, the speed of biosorption of target spe-
cies with respect to the removal efficiency, the possi-
bility of regenerating the biosorbent and reusing it.
2.1.1. Algae as biosorbents
Algae are divided into two main types: micro-algae
and macro-algae. Macro-algae, which are also known
as seaweeds, are multi cellular plants that grow in
fresh or salt water, they are classified based on their
pigmentation, which includes three groups: brown,
red and green algae (Anastopoulos & Kyzas, 2015).
On the other hand, micro-algae are photosynthetic
unicellular plants that also grow in fresh or salt
water, they are classified based on their pigmenta-
tion, arrangement(s) of their photosynthetic mem-
branes or other morphological features
(Anastopoulos & Kyzas, 2015). The four groups of
micro-algae are diatoms, green algae, golden algae
and blue-green algae (cyanobacteria) (Anastopoulos
& Kyzas, 2015). The high biosorption ability of algae
is due to the composition of their cell wall that is
comprised on chitin, polysaccharides, proteins and
lipids which contain vital functional groups aiding in
biosorption (Davis, Volesky, & Mucci, 2003).
Functional groups containing oxygen, nitrogen, sul-
phur and phosphorus were found to be the main
contributors in biosorption of heavy metals by algae
(Iv
anov
a, Kadukov
a, Kavulicov
a, & Horv
athov
a, 2012).
Considering macro-algae, brown algae have cell
walls mainly composed of cellulose, alginic acid, pol-
ymers (such as mannuronic and guluronic acids)
which are complexed with light metals (such as
sodium, potassium and calcium), and polysaccharides
(e.g., fucoidan) (He & Chen, 2014). Alginate and
fucoidan have the potential of metal binding by ion
exchange, the main biosorption binding sites in
alginate contain carboxyl groups and secondly sul-
phate groups (Iv
anov
a et al., 2012). The main con-
tent of green algae cell walls are proteins, which
include functional groups such as amino, carboxyl,
hydroxyl and sulphate that contribute in metal bio-
sorption (Iv
anov
a et al., 2012). On the other hand,
red algae have cell walls mainly comprised of cellu-
lose, nevertheless, their biosorption capacity lies in
the presence of sulphated polysaccharides made up
from galactans (He & Chen, 2014). Micro-algae
slightly differ in their cell wall composition, as they
mainly contain polysaccharides, proteins and lipids,
these components contain carboxyl, hydroxyl, phos-
phate and sulphate groups that provide an overall
negative net charge on the cell surface, favouring
the binding of metal cations through counter ion
interactions (Anastopoulos & Kyzas, 2015).

Out of all types of algae and other biosorbents,
brown algae has shown the most significant biosorp-
tion capacities towards different metal ions (Akbari,
Hallajisani, Keshtkar, Shahbeig, & Ali Ghorbanian,
2015). Moreover, using brown algae has additional
advantages as it is available in large quantities, has a
high surface area to volume ratio and high efficiency
in dilute effluents, has the possibility of regenerating
and recovering biosorbed metal, and produces less
sludge (Akbari et al., 2015). Overall, algae is the most
common biosorbent used compared to other bio-
sorbent due to its high availability, relative cheap
processing costs and high performance (Al-
Homaidan, Al-Houri, Al-Hazzani, Elgaaly, & 2019). According to this study, oxygen-containing
Moubayed, 2014).
A research evaluated the removal of cadmium(II)
and lead(II) from aqueous solution by blue green
alga Anabaena sphaerica (Abdel -Aty, Ammar, Abdel
Ghafar, & Ali, 2013). The results suggested that this
alga has a relatively high biosorption capacities for
the removal of cadmium(II) and lead(II), calculated to
be 111.1 mg/g and 121.95 mg/g, respectively (Abdel
-Aty et al., 2013). The Fourier transform infrared
(FTIR) analysis of algal surface functional groups, sug-
gested that the amino, carboxyl, hydroxyl, and car-
bonyl groups were responsible for biosorption of
those ions (Abdel -Aty et al., 2013). Another research
studied the ability of chemically modified Cystoseira
indica in the biosorption of uranium(VI) oxide and
lead(II) cations (Moghaddam, Fatemi, & Keshtkar,
2013). In addition, Sargassum biomass was found
capable of biosorption of cadmium and lead cations
by partial or complete esterification of carboxylic
sites present on its cell wall (Abdi & Kazemi, 2015).
2.1.2. Bacteria as biosorbents
Bacteria are classified as gram-positive bacteria or
gram-negative bacteria, the most significant differ-
ence between these two types is in their cell wall
composition and thickness (Zyoud et al., 2019). The
cell wall of gram-positive bacteria have thicker pep-
tidoglycan layers which are connected by amino acid
bridges (Zyoud et al., 2019)(Abdi & Kazemi, 2015).
Gram-positive bacteria have greater potential of
removal of heavy metal cations due to the signifi-
cant electronegative charge density they hold due to
the presence of teichoic and teichuronic acids (poly-
alcohol) which are linked by phosphodiester bonds,
attached to peptidoglycan of the cell wall (Tsezos et
al., 2014; Abdi & Kazemi, 2015).
Functional groups containing oxygen, nitrogen,
sulphur or phosphorus are the common contributors
of heavy metal biosorption in bacteria (Javanbakht
et al., 2014). A research studying biosorption of
lead(II) ions by Aeromonas hydrophila suggested,
with the aid of FTIR spectral data, that the carboxyl,
ARAB JOURNAL OF BASIC AND APPLIED SCIENCES 185
hydroxyl and amine groups of the biosorbent surface
contributed in removal of lead(II) ions from water
(Javanbakht et al., 2014). A very recent research
studied the biosorption of uranium(VI) onto Bacillus
amyloliquefaciens, the functional groups contributing
in removal of uranium(VI) were analysed by FTIR and
XPS (Liu et al., 2019). After biosorption of
uranium(VI) by the bacterium, a new peak appeared
in the FTIR spectra of the biosorbent as a result of
anti-symmetric vibration of [O ¼ U¼O]2þ group (Liu
et al., 2019). The XPS results also suggested the for-
mation of chemical binding between uranium and
oxygen-containing functional groups (Liu et al.,
functional groups were the main site of biosorption
of uranium(VI).
2.1.3. Fungi as biosorbents
Fungi started to receive more attention as a biosorb-
ent recently due to the rich cell wall content, which
suggests the presence of a wide range functional
groups which be involved in metal removal (Benila
Smily & Sumithra, 2017). The fungal cell wall is com-
prised of chitin, cellulose, b-glucan, a-glucan, chito-
sans, polyuranides, glucoproteins, lipids, inorganic
salts and pigments (Dhankhar & Hooda, 2011).
Comparing the usage of fungi as biosorbents with
algae and plants, fungal biomass is easy cultivated in
large scales and it is easily grown by simple fermen-
tation techniques with overall low costs (Dhankhar &
Hooda, 2011). A research studied the functional
groups of Mucor rouxii contributing in biosorption of
lead, cadmium, nickel and zinc (Yan & Viraraghavan,
2008). It was found, by the aid of FTIR, that amine
and phosphate groups were the main contributors
in the biosorption process, while role of lipid fraction
was not vital (Yan & Viraraghavan, 2008).
2.1.4. Plants as biosorbents
Plants, as agricultural waste materials and food
industries discarded material have been used as bio-
sorbents, it is a form of reusing and recycling those
waste materials thus no significant costs are associ-
ated with using plant materials. The potential of
plant biosorbents are mainly due to the presence of
carboxylic and phenolic functional groups in the cel-
lulosic matrix or components associated with cellu-
lose such as lignin and hemicellulose (Abdi &
Kazemi, 2015). Aloe vera wastes were used as bio-
sorbent for the removal of uranium and cadmium
from water, it was found that the carboxyl, carbonyl
and hydroxyl groups facilitated metal binding (Noli,
Kapashi, & Kapnisti, 2019).
186 A. ALI REDHA
Table 1. Comparison between biosorption capacity of different biosorbents for removal of lead(II) ions from aqueous media.
Biosorbent Biosorbent Type
Pokeweed (untreated) Plant
Pokeweed (treated with nitric acid) Plant
Durian tree sawdust Plant
Olive tree pruning (untreated) Plant
Coconut coir Plant
Oil palm empty fruit bunch Plant
Peanut shells Plant
Cyclosorus interruptus Plant (Fern)
Olive tree pruning (treated with sulphuric acid) Plant
Olive tree pruning (treated with nitric acid) Plant
Olive tree pruning (treated with sodium hydroxide) Plant
Anabaena sphaerica Algae
2.2. Biosorption of selected heavy metals
2.2.1. Biosorption of lead
Lead is a heavy transition metal. The approximated
concentration ranges of discharged lead(II) ions in
the environment from battery industry is 5-66 mg/L,
from mining industry is 0.02-2.5 mg/L and that from
€ wastewater before discharging it in the environment.
the oil industry is 125-150 mg/L (Taşar, Kaya, & Ozer,
2014). Lead is considered lethal to animals and
plants (Nadeem, Manzoor, Iqbal, & Nisar, 2016). It
causes several illness for humans, such as anaemia,
brain damage, mental deficiency, kidney damage,
encephalopathy, anorexia, cognitive impairment,
behavioural issues and vomiting (Nadeem et al.,
2016)(Morosanu, Teodosiu, Paduraru, Ibanescu, &
Tofan, 2017). Lead(II) ions have high affinity to thio,
oxo and phosphate groups that are present in some
enzymes and biomolecules in living organisms
(Morosanu et al., 2017). In humans, binding of lead
to those enzymes can change the cellular membrane
permeability of organs and haemoglobin synthesis, it
can also bioaccumulate in bones (its half-time is
over 20 years) (Morosanu et al., 2017). Thus, it is
highly important to remove lead from wastewater
before discharging it in the environment. Several
studies were conducted evaluating the capacity of
different biosorbents for the removal of lead(II) ions
from aqueous media, selected studies are presented
in Table 1, comparing the biosorption capacity
of each.
2.2.2. Biosorption of chromium
Chromium, a toxic, carcinogenic, mutagenic and
teratogenic heavy metal, which usually exists as tri-
valent and hexavalent forms in aqueous environ-
ment (Rezaei, 2016). Chromium is one of the main
pollutants in surface water and groundwater, espe-
cially its hexavalent form due its high mobility and
solubility in aqueous environment, the hexavalent
form is also about 500 times more toxic than triva-
lent form (Mishra, Dubey, & Shinghal, 2015). In
humans, it can be a cause of allergic reaction,
respiratory disorders, weakness of immunity system
and kidney, liver and gastric damage (Netzahuatl-
Mun ~oz, Del Carmen Cristiani-Urbina, & Cristiani-
Maximum Biosorption Capacity (mg/g) Reference
13.19 (Wang et al., 2018)
14.51 (Wang et al., 2018)
20.37 (Yusoff et al., 2014)
27.05 (Calero et al., 2013)
37.04 (Yusoff et al., 2014)
37.59 (Yusoff et al., 2014)
39 (Taşar et al., 2014)
46.25 (Zhou, Yang, Liu, & Kong, 2015)
65.62 (Calero et al., 2013)
85.09 (Calero et al., 2013)
121.06 (Calero et al., 2013)
121.95 (Abdel -Aty et al., 2013)
Urbina, 2015). The main industrial sources of chro-
mium are electroplating, textile and metal finishing
industries, iron and steel foundries, inorganic chem-
ical plants and tanneries (Mishra et al.,
2015)(Netzahuatl-Mun ~oz et al., 2015). It is highly
important that industries remove chromium from
Several studies were conducted evaluating the cap-
acity of different biosorbents for the removal of dif-
ferent forms of chromium from aqueous media,
selected studies are presented in Table 2, comparing
the biosorption capacity of each.
2.2.3. Biosorption of cadmium
Cadmium accumulates in photosynthetic plants and
fish, which can then be easily transferred to humans
(Al-Homaidan, Alabdullatif, Al-Hazzani, Al-Ghanayem,
& Alabbad, 2015). Cadmium has the potential to
bind with cysteine, glutamate, histidine and aspar-
tate ligands in the human body causing iron defi-
ciency (Jaishankar et al., 2014). When cadmium binds
to cysteine-rich proteins such as metallothionein in
the liver, the complex formed can cause hepatotox-
icity and upon circulation and transport to the kid-
ney it can accumulate in the renal tissue causing
nephrotoxicity (Jaishankar et al., 2014). The polluting
sources of cadmium are electroplating, smelting,
paint pigments, batteries, fertilizers, mining and alloy
industries (Ghoneim et al., 2014). Table 3 compares
the biosorption capacity of different biosorbents
studied for the removal of cadmium ions.
2.3. Mechanisms of biosorption
Heavy metals are taken up by the biosorbent
through several mechanisms, different literatures
suggested different mechanisms based on the type
of biosorbent and classification criteria. Besides, most
mechanisms are not fully understood in detail due
to complexations in the biological nature of the bio-
sorbents. The mechanisms are either classified
according to (a) the dependence on cell metabolism
or (b) the location within the cell where the metal is
removed which is divided into three types: extra cel-
lular accumulation/precipitation, cell surface
 ARAB JOURNAL OF BASIC AND APPLIED SCIENCES 187

Table 2. Comparison between biosorption capacity of different biosorbents for removal of chromium ions from aqueous media.
Biosorbent Biosorbent Type Chromium Sorbate Maximum Biosorption Capacity (mg/g) Reference
Opuntia ectodermis Plant Cr(VI) 16.4 (Fern
andez-L
opez, Angosto, & Avil
es, 2014)
Opuntia cladodes Plant Cr(VI) 18.5 (Fern
andez-L
opez et al., 2014)
Portulaca Oleracea Plant Cr(VI) 54.95 (Mishra et al., 2015)
Spirulina sp. Algae Cr(VI) 90.91 (Rezaei, 2016)
Pleutrotus sajor-caju Fungi Cr(VI) 122.36 (Hanif, 2011)
Ganoderma lucidum Fungi Cr(VI) 127.28 (Hanif, 2011)
Agaricus bitorquis Fungi Cr(VI) 127.92 (Hanif, 2011)
Pleutrotus sajor-caju Fungi Cr(III) 141.88 (Hanif, 2011)
Ganoderma lucidum Fungi Cr(III) 149.58 (Hanif, 2011)
Agaricus bitorquis Fungi Cr(III) 152.74 (Hanif, 2011)
Chlorella vulgaris Algae Cr(VI) 161.41 (Sibi, 2016)
Watermelon rind Plant Cr(III) 172.6 (Reddy, Lakshmipathy, & Sarada, 2014)
Aspergillus flavus Fungi Cr(III) 257 (Azhar & Iram, 2014)
Cupressus lusitanica bark Plant Cr(VI) 305.4 (Netzahuatl-Mun ~oz et al., 2015)

Table 3. Comparison between biosorption capacity of different biosorbents for removal of cadmium(II) from aqueous media.
Biosorbent Biosorbent Type Maximum Biosorption Capacity (mg/g) Reference
Ulva lactuca Algae 29.1 (Ghoneim et al., 2014)
Streptomyces rimosus Bacteria 64.9 (Sahmoune, 2018)
Saccharomyces cerevisiae Fungi 68.78 (Farhan & Khadom, 2015)
Aloe vera waste Plant 104.2 (Noli et al., 2019)
Anabaena sphaerica Algae 111.1 (Abdel -Aty et al., 2013)
Klebsiella sp. Bacteria 170.4 (Hou et al., 2015)

sorption/precipitation and intracellular accumulation
(Ahalya, Ramachandra, & Kanamadi, 2003). Very
recently, the biosorption based on cellular metabol-
ism has been referred to as bioaccumulation rather
than a type of biosorption (Bilal et al., 2018). The
mechanisms of cell metabolism dependent biosorp-
tion or bioaccumulation are transport across cell
membrane and precipitation, while the mechanisms
of cell metabolism independent biosorption are pre-
cipitation, physical adsorption, ion exchange and
complexation (Figure 1) (Perpetuo, Souza, &
Nascimento, 2011). Looking at the second criteria,
extra cellular accumulation/precipitation is achieved
by transport across cell membrane; while cell surface
sorption/precipitation is achieved through ion
exchange, complexation, physical adsorption and
precipitation; finally, intracellular accumulation is
achieved by precipitation (Figure 1) (Perpetuo et al.,
2011). Simple diffusion is also a basic mechanism
observed in most types of biosorption (Sao, 2014).
Several factors can contribute in controlling the
mechanisms, those include the chemical, stereo-
chemical and coordination characteristics of the
metal of interest which involves the ion mass, ionic
radius and the oxidation state of the metal ion
(Kanamarlapudi, Chintalpudi, & Muddada, 2018). The
properties of the biosorbent of choice also affect
the mechanism of biosorption, properties such as
the number of reactive binding sites, accessibility
and availability of binding sites, type of binding site
and the affinity between the binding site of the bio-
sorbent and metal ion of interest (Abdi & Kazemi,
2015). There are other factors which are based on
the environmental conditions that biosorption is tak-
ing place such as pH, temperature and complexity of
solution containing the metal ion (Kanamarlapudi
et al., 2018). In some cases, more than one mechan-
ism may take place in a multi-step process mechan-
ism, biosorption of uranium by Aloe vera waste
involved physical adsorption, ion exchange, complex-
ation and precipitation (Noli et al., 2019).
2.3.1. Physical adsorption
Physical adsorption takes place on the surface of the
biosorbent, possibly with the cell walls while dealing
with microorganisms, with the aid of electrostatic
interactions such as Van der Waals forces. Physical
adsorption mechanism is affected by the surface
area of the biosorbent and in some cases the pH of
solution (Chojnacka, 2006) (Bashir et al., 2019). In the
biosorption of lead by hami melon peels, physical
adsorption was only favoured at basic conditions
with the contribution carboxylate and hydroxylate
groups of the biomass (Bashir et al., 2019). A study
suggested that chromium(III) ions were biosorbed by
grass and wheat straw through physical adsorption
mechanism bounded in a monolayer form, based on
calculated maximum biosorption capacity and know-
ledge of ionic radius of the metal (Chojnacka, 2006).
It has also been reported that the Zoogloea ramigera
(bacterium) and Chiarella vulgaris (alga) are capable
of biosorbing copper ions by physical adsorption
(Perpetuo et al., 2011).
2.3.2. Ion exchange
Ion exchange process is the replacement of an ion
bounded into the solid phase which is readily-
exchangeable with another ion in solution (Gadd,
2009). Considering the biosorption in microorgan-
isms such as bacteria and fungi, it has been found
188 A. ALI REDHA
Figure 1. Classification of Biosorption Mechanisms.
that Gandoderma lucidium biosorbs copper ions by
ion exchange mechanism; this is possible in microor-
ganisms due to the composition of their cell walls
which have polysaccharides that can ion exchange
with their counter ions (Perpetuo et al., 2011). It has
been reported that upon binding of heavy metal
ions such as copper(II), cadmium(III) and zinc(II) to
alginate of brown algae, an enhanced release of cal-
cium, potassium, magnesium and sodium was
observed due to ion exchange mechanism (Abdi &
Kazemi, 2015)(Ahalya et al., 2003). A study reported
that rice straws, as an example of non-metabolism
dependent biosorbent, were able to biosorb
cadmium(II) ions by ion exchange with sodium,
potassium, magnesium and calcium (Kanamarlapudi
et al., 2018). In addition, it was found that pH of
solution can affect some biosorption mechanisms
such as ion exchange. The biosorption mechanism of
lead ions by hami melon peels was achieved by ion
exchange at low pH, while at higher pH it was
achieved by electrostatic interactions between carb-
oxylate and hydroxylate groups on the biomass and
lead ions (Bashir et al., 2019). Spirulina, a cyanobac-
teria, was capable of biosorbing chromium(III),
cadmium(II) and copper(II) through ion exchange by
identified functional groups including carboxyl, phos-
phate and hydroxyl groups (Kanamarlapudi
et al., 2018).
2.3.3. Complexation
Complexation is a process of complex formation by
electrostatic attraction or covalent bonds between
metal ions and organic molecules acting as ligands
with the ability to donate electrons, the advanced
form of complexation is chelation in which the
organic ligand would bond coordinatively with the
metal ion from more than one position at the same
time to form a complex of higher stability (Tsezos et
al., 2014). The affinity of metal ion and organic lig-
and, which is the most significant factor in complex-
ation, is based on the Hard and soft acids and bases
(HSAB) theory, which implies that elements are clas-
sified into hard or soft acids (mainly metals) and
hard or soft bases (mainly non-metals), hard acids
have stronger affinity to hard bases and so the weak
acids and bases (Ayers, 2005). Lead being a soft acid,
would favour binding covalently to organic ligands
of the biosorbent containing nitrogen or sulphur
which are soft bases; manganese, zinc, cadmium and
copper ions which are classified as borderline ions
(hard/soft) also have a high affinity to form com-
plexes with nitrogen or sulphur containing organic
compounds (Tsezos et al., 2014). Nevertheless, com-
plexation is affected by the accessibility and avail-
ability of the binding site containing the donor atom
(base). Desorption studies using scanning electron
microscopy (SEM), transmission electron microscopy
(TEM) and energy dispersive X-ray spectroscopy
(EDX) can confirm if biosorption mechanism is
achieved by complexation (Han, Wong, & Tam,
2006). Using those methods, the biosorption mech-
anism of chromium(III) by Chlorella miniate, a green
microalgal, was confirmed to be through complex-
ation by carboxyl, phosphonate and amine ligands
(Han et al., 2006).
2.3.4. Precipitation
Precipitation refers to the formation of insoluble
metal in the form of precipitate, which is one of the
few mechanisms involved in the metabolism
dependent biosorption, nevertheless metabolism
independent biosorption can also occur by precipita-
tion. In the metabolism dependent biosorption, pre-
cipitation occurs as a response by the
microorganisms’ active defence system in the pres-
ence in an environment containing toxic metal ions
(Perpetuo et al., 2011). In the metabolism independ-
ent biosorption, precipitation occurs due to chemical
reactions between the functional groups of the cell
wall of the biosorbent and the metal ion, the reac-
tions may involve oxidation-reduction reactions
(Kanamarlapudi et al., 2018). A study confirmed the

Figure 2. Speciation of Cr(III) in different pH at 25˚C and con-
centration of 10 mg/L, adapted from (Bl
azquez et al., 2009).
mechanism of the removal of iron(III) ions from
aqueous solution by the aid of green tomato husk
to be mainly via precipitation and ion exchange
(Garc
ıa-Mendieta, Olgu
ın, & Solache-R
ıos, 2012).
Iron(III) ions precipitated in the form of iron(III)
hydroxide at pH 6.0 (Garc
ıa-Mendieta et al., 2012).
2.3.5. Transport across cell membrane
Transport of heavy metal ions across cell membrane
is a mechanism usually observed in microorganisms
only. This mechanism comprises of two stages: in
the first stage the metal ion binds to binding sites
on the cell wall of the microorganism which is
referred to as independent binding metabolism,
then in the second stage the metal ion is trans-
ported across the cell membrane into the cell and
this step is referred to as metabolism dependent
intracellular uptake (Perpetuo et al., 2011). The
mechanism mimics the process of uptake of essential
ions by the cell, it has been mentioned that cellular
metal transport systems are tricked by heavy metal
ions having the similar ionic radius and charge of
the essential metal ions, nevertheless the process is
not clearly understood yet (Perpetuo et al., 2011).
2.4. Factors affecting biosorption capacity
2.4.1. pH
The pH under which biosorption takes place is very sig-
nificant and directly affects the biosorption capacity,
and in some cases the mechanism via which biosorp-
tion takes place as mentioned earlier. pH affects both
the chemistry of the functional groups of biosorbent
and the chemistry of metal ions (Wei et al., 2016). The
biosorption capacity often increases with the increase
of pH until it reaches the optimum pH where the max-
imum biosorption capacity is observed, following that,
upon further increase in pH, metals begin to precipitate
due to formation of metal hydroxides or hydroxide
anionic complexes (Abdi & Kazemi, 2015)(Bilal et al.,
2018). The biosorption of metal ions such as copper,
ARAB JOURNAL OF BASIC AND APPLIED SCIENCES 189
cadmium, nickel, cobalt and zinc are usually reduced at
low acidic pH conditions, in which competition occurs
between the metal cations and hydronium ions for the
binding sites of the biosorbent (Gadd, 2009). At low
pH, the functional groups of the biosorbent would
favour the hydronium ions as the functional groups
exist in protonated form and repulsive forces between
the functional groups and metal cations would not
allow attraction of those two, however as the pH
increases, functional groups such as carboxyl, hydroxyl,
phosphate groups would start experiencing negative
charges (and amino and imidazole groups turning neu-
tral) due to deprotonation, this would increase binding
of metal cations and thus increase the biosorption cap-
acity and speed of biosorption (Abdi & Kazemi,
2015)(Bilal et al., 2018). Although increasing pH further
would ensure that all the acidic groups are deproto-
nated, however the free metal cations can start to pre-
cipitate as metal hydroxides, decreasing the efficiency
of removal of the metal.
As mentioned earlier, pH does not only affect the
functional groups of the biosorbent, it also affects
the chemistry of metal ions. pH would affect the
form of the metal ion present in aqueous solution
and the concentration of that form, resulting in the
formation of different metal ion species at different
pH levels. In a study considering the biosorption of
chromium(III) ions by olive stones, the speciation of
chromium(III) ion was analysed (Figure 2) (Bl
azquez,
Hern
ainz, Calero, Mart
ın-Lara, & Tenorio, 2009). As
shown in Figure 2, it suggests that chromium(III)
would be present in five different forms: Cr3þ,
Cr(OH)2þ, Cr(OH)2þ, Cr(OH)4- and a solid form
Cr(OH)3 as a precipitate. The dominant form of
chromium(III) varies according to the pH. Different
species would have different affinity to the func-
tional groups of the biosorbent, this would affect
the biosorption process. In addition, the solubility
and mobility of metal ion species differ and this will
also have an impact on biosorption process
(Gadd, 2009).
2.4.2. Temperature
Temperature affects the surface activity of the bio-
sorbent and thus the biosorption capacity. The effect
of temperature on the biosorption process depends
on the nature of the process. Increasing the tem-
perature for an exothermic biosorption process
would result in a decrease in metal ion removal, the
opposite is true for endothermic biosorption proc-
esses (Taşar et al., 2014). Likewise, decreasing the
temperature for an exothermic biosorption process
would result in an increase in metal ion removal, the
opposite is true for endothermic biosorption proc-
esses. Biosorption is not highly affected between
changes in temperatures ranging from 20˚C up to
190 A. ALI REDHA
Figure 3. Effect of contact time on biosorption capacity of
A. niger for the removal of Zn(II), Co(II) and Cd(II) at pH 7,
biomass dosage of 2 g/L and initial ions concentration of
10 mg/L, adapted from (Hajahmadi et al., 2015) research.
35˚C (Sao, 2014)(Perpetuo et al., 2011). The biosorp-
tion of lead(II) ions by peanut shells decreased with
increasing temperature, suggesting the exothermic
nature of the process (Taşar et al., 2014).
2.4.3. Contact time
Contact time usually refers to the time allocated for
biosorption process to take place. Biosorption cap-
acity is not directly affected by contact time of the
biosorbent and sorbate, however it can act as a limit-
ing factor. Under experimental conditions, increasing
contact time would allow the biosorbent material to
unveil the maximum biosorption capacity. When the
biosorbent reaches its maximum biosorption capacity
at defined conditions its binding sites become fully
saturated, increasing contact time would not have any
further effect as shown in Figure 3 (Hajahmadi,
Younesi, Bahramifar, Khakpour, & Pirzadeh, 2015).
2.4.4. Biomass dosage
At low biomass dosage an increase in the specific
uptake of metal ions has been observed (Sao,
2014)(Perpetuo et al., 2011). Nevertheless, using low
biomass dosage in complex contaminated water
would increase competition for binding site of bio-
sorbent and will limit the biosorption capacity of the
biosorbent. Increasing the biomass dosage would
decrease the competition between metal ions pre-
sent for binding to the functional groups, specifically
when more than one metal ion is present. In most
of the published researches, the amount of biomass
used was between 0.5 -6.0 g/L.
2.4.5. Initial metal concentration
In a study evaluating the potential of banana peel as
a biosorbent for heavy metals, it was found that the
metal biosorption increases when the initial metal
concentration increases (Ashraf, 2011). Increasing ini-
tial metal concentration, has a similar effect as
increasing contact time. Using low metal concentra-
tion would not unveil the true maximum biosorption
capacity of the biosorbent, as many metal binding
sites may not be occupied. Increasing the metal con-
centration up to full saturation of binding sites of
the biosorbent would reveal the full potential of
metal removal. Upon saturation of biosorbent, fur-
ther increasing the initial metal concentration will
not be effective. In most of the published researches,
the initial metal concentration used in experimental
conditions was 5-200 mg/L.
2.4.6. Other factors
Surface area of the biosorbent material affects the
biosorption capacity of the biosorbent, higher sur-
face area would increase biosorption under the same
conditions. A study compared the biosorption of
lead, copper and zinc ions by (a) dried lettuce leaves
and (b) powdered lettuce leaves (in dry form), under
all conditions, the metal removal by powdered let-
tuce leaves was higher than dried leaves
(Shartooh, 2013).
The presence of more than one metal ion in the
same media can influence the removal of one metal
ion on another, as one metal ion could have higher
affinity to the binding sites of the biosorbent leading
to competition on the availability of binding sites
(Sao, 2014).
Researches have studied the effect of chemical
modifications on the biosorption capacity of the bio-
sorbent material. A study evaluating the biosorption
of lead(II) ions by untreated and chemically treated
olive tree pruning suggested that chemically modi-
fied biosorbent samples had a higher biosorption
capacity (as numerically outlined in Table 1) (Calero,
P
erez, Bl
azquez, Ronda, & Mart
ın-Lara, 2013). The
infrared spectra data and potentiometric titrations
suggested that the surface of acid treated samples
contained more acidic groups than the untreated
sample, indicating that the surface of the treated
biosorbent became more negative due to the dis-
sociation of weakly acidic oxygen containing func-
tional groups that contribute in biosorption resulting
in higher biosorption capacity (Calero et al., 2013).
2.5. Desorption
Upon the completion of biosorption, the exhausted
biosorbent can be reused by removal of the bio-
sorbed metal ions and safely discarding them, this
process is known as desorption and is achieved with
the aid of a desorbing agent (Benila Smily &
Sumithra, 2017). The role of desorbing agent is to
desorb the biosorbed species from the biosorbent,
and ultimately regenerate the biosorbent for further

use. The percentage of desorbed species is calcu-
lated according to the following equation:
Desorption Percentage (%) ¼ (Amount of Species
Desorbed  Amount of Species Loaded) x 100%
High desorption percentage suggests higher
degree of regeneration of biosorbent for further use,
this should also be considered while choosing the
biosorbent for greater degree of sustainability.
Desorbing agents are commonly divided into
three groups: acids (such as hydrochloric acid, sul-
phuric acid, nitric acid and acetic acid), alkalis
(sodium hydroxide, sodium hydrogen carbonate,
sodium carbonate and potassium hydroxide) and
chelating agents (such as ethylenediaminetetraacetic
acid) (Lata, Singh, & Samadder, 2015). Acidic desorb-
ing agents have been found to be more efficient
than basic and neutral agents in terms of speed and
desorption percentage (Lata et al., 2015). A good
desorbing agent should not alter the chemical and
physical properties of the biosorbent.
2.6. Critical analysis of biosorption
Biosorption is economically feasible, easy to operate
and use, and shows good adsorption efficacy (Wei
et al., 2016). Biomass can be obtained from waste
and discarded plant products (e.g., peels and stones)
or can be obtained from fermentation industries
which consider them as waste, thus no costs are
associated with their provision (Abdi & Kazemi,
2015). Using biosorption methods can be very useful
in developing countries with low technological
development. Plant biosorbents also have the advan-
tage of minimizing chemical and/or biological sludge
(Ashraf, 2011). The usage of many types of biosorb-
ents are in compliant with sustainable development
as the biosorbent can undergo desorption and be
regenerated, besides adding the possibility of recov-
ering the metal for further industrial uses.
Many research papers have studied the removal
of one to two metals by biosorption, however the
results obtained by these researches may not be
applicable in real life situations in which contami-
nated water as a wide range of heavy metals can be
present in contaminated water. In fact, organic pollu-
tants may also be present in water, which can also
affect the nature of metal ions and their biosorption
process. A recommended phase in biosorption stud-
ies can be studying the applications of laboratory
findings on real contaminated water samples. For
example, water pH, being the most influential factor,
would be challenging to optimise in real life situa-
tions due to the presence of a wide range of other
environmental factors affecting pH, thus biosorption
capacities of biosorbents determined for specific pH
levels under laboratory conditions may not be true
ARAB JOURNAL OF BASIC AND APPLIED SCIENCES 191
in real life. The water samples experimented usually
do not reflect complexity and matrix nature of real
contaminated water.
In addition, the main focus of most researches
dealing with biosorption is the removal of heavy
metals, however removal of toxic organic pollutants
has not been studied in depth. In fact, a lot of
researches are based on removal of heavy metals in
their cationic form and not the anionic (e.g., CrO42-).
One of the limitations of biosorption process could
be the early saturations of biosorbent, thus biosorb-
ent shall be frequently replaced. The saturated bio-
sorbent shall be desorbed from the biosorbed metal
and the recovered metal shall be safely disposed.
The efficiency of desorption process and efficiency of
recycled/reused biosorbent can be negotiable too.
According to Clarivate Analytics, from 1951 up to
13/04/2019, 14,841 papers with “biosorption” as a
topic, were published. Unfortunately, the use of bio-
sorbent is still not commercialised by the industries
(Gadd, 2009). Industries tend to favour using meth-
ods including chemical precipitation, ion exchange,
oxidation-reduction methods and reverse osmosis
(Gadd, 2009). Chemical precipitation is highly fav-
oured due to its significant efficiency in the removal
of a wide range of heavy metals (it is not selective),
nevertheless this method produces high amounts of
solid sludge which is not environmentally favourable
(Gadd, 2009). Another challenge facing implementa-
tion of biosorption in industries is that their current
methods, such as precipitation and ion exchange,
are very well established into their processes and
have proven their applicability on large scales.
Industries might find it risky and infeasible to replace
their current trusted method with new methods.
3. Conclusions
Biosorption methods can be an alternative to the
common industrial methods of removal of heavy
metals due to being environmentally friendly and
sustainable for use. Several types of biosorbent
materials can be used such as algae, bacteria, fungi
and plants. Biosorption process can take place by
several mechanisms including physical adsorption,
ion exchange, complexation, precipitation and trans-
port across the cells. The biosorption capacity of bio-
sorbents can be affected by the pH of the
environment, temperature, contact time, biomass
dosage, initial metal concentration and other factors.
A major limitation of the researches conducted in
this area, studying the biosorption capacity of differ-
ent biomass, is that they did not encounter for the
complexity of real-life contaminated water.
192 A. ALI REDHA
Disclosure statement
No potential conflict of interest was reported by
the author(s).
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