Suez Canal University

Faculty of Science
Chemistry Department

Application of Biosorption for removal of

heavy metals from waste water

A research Project presented by

Rawan Ghareeb Maghraby

4th level Credit Hour Chemistry Department

Supervisor:
Dr. Hoyeda El-Sayed Ibrahim
Assistant professor of physical chemistry

2024

1
 Acknowledgements

After thanking Allah for his blessing and Praying on his Chosen prophet I,d like to

Express my thanks and Deep gratitude to Dr .Hoyeda Ibrahim For The effort

Exerted during The Preparation of This Article I’d like to thank her for her Patience

and tolerance and her elegant way in dealing with me. No matter what I can say it

will never be enough ,To Express what I really owe her.

By Rawan Gharib.

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 Contents

Subject Page No.

Acknowledgements 2

Chapter (1)
"Heavy Metal Toxicity and Biosorption: Insights"
1. Introduction 6
2. Toxicity of heavy metals 8
3-Bioaccumulation and biosorption 9
3.1. Bioaccumulation 9
3.2. Biosorption 11
4.Mechanism of biosorption 12
4.1 Complexation 14
4.2 Chelation 14
4.3. Coordination 15
4.4. Ion exchange 15
4.5. Precipitation 16
4.6. Reduction 17
5.Advantages and Disadvantages of Biosorbtion 17

Chapter2:
"Exploring Factors in Batch Biosorption Experiments"
6• Batch experimental 19
6.1:Factors influencing batch biosorption 19
6.1.1Effect of pH 20
6.1.2Effect of temperature 20

3
6.1.3Effect of Ionic strength 20
6.1.4. Effect of initial pollutant concentration 20
6.1.5. Effect of biosorbent dosage 20
6.1.6 Effect of biosorbent size 21
6.1.7 Effect of agitation speed 21
6.1.8Effect of Other pollutant concentration 21
7. A comparison between different biosorbents. 21
8. Desorption and the regeneration of biosorbent 25
9-Experimental methods and techniques 27
10..Biosorption equilibrium isotherms 28
11.Bioreactors used for biosorption 29

Chapter3:
"Biosorption in Industry: Present and Future"
12.Industrial Applications 30
13-Commercialization and adoption of biosorption as waste 31
treatment technology
14-Future perspectives and research directions for 32
adsorption of heavy metals from wastewater
Chapter 4
15-Conclusions 34
16-Reference 38

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 List of Figure
figure Page No.
Fig. Figure1: Heavy metals can damage living things At low conc 8
and tend to accumulate in the food chain

Figure 2 :types of heavy metals 9

Figure 3: Biosorption mechanism 13
Figure 4: Chelation 15
Figure 5:Ion exchange for waste water treatment 16
Figure6:precipitation for waste water treatment 16
Figure 7: batch experiment system 19
Figure 8. Algae biosorbents heavy metals 23
Figure 9: Biosorption mechanisms of copper, cobalt and other 24
heavy metals by filamentous fungi

List of table

Table Page No.

Table:1 summarizes some more examples of biosorbents 10
used for metal bioaccumulation.
Table 2. Use of different eluents for desorption of metal 26
ions.

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 Chapter 1
"Heavy Metal Toxicity and Biosorption: Insights"

1. Introduction

Water plays an important role in the world economy. Majority (71%) of the Earth’s
surface is covered by water, but fresh water constitutes a miniscule fraction (3%) of
the total. Water fit for human consumption is obtained from the fresh water bodies.
Approximately, 70% of the fresh water goes to agriculture. This natural resource is
becoming scarce at many places and its unavailability is a major social and economic
concern [1]. Though access to safe drinking water has improved over the last few
decades, it is estimated that five million deaths per year are caused due to
consumption of polluted drinking water or drought. In many developing countries,
90% of all wastewater still goes untreated into the fresh water bodies making it unfit
for human consumption, which either leads to scarcity or affects the human
population [2]. The concern to protect fresh water bodies for a healthy population is a
challenge in recent times.
Industrialization to a larger degree is responsible for the contamination of
environment especially water where lakes and rivers are overwhelmed with a large
number of toxic substances. Heavy metals are reaching hazardous levels when
compared with the other toxic substances [3]. Heavy metals are a unique group of
naturally occurring compounds. Their continuous release leads to overconsumption
and accumulation. As a result, people around the globe are exposed to adverse
consequences of these heavy metals. Many industries (fertilizers, metallurgy, leather,
aerospace, photography, mining, electroplating, pesticide, surface finishing, iron and
steel, energy and fuel production, electrolysis, metal surface treating, electro-osmosis,
and appliance manufacturing) discharge waste containing heavy metals either directly
or indirectly into the water resources [4]. Toxic heavy metals, which are of concern,
are chromium (Cr), lead (Pb), zinc (Zn), arsenic (As), copper (Cu), nickel (Ni), cobalt
(Co), cadmium (Cd), mercury (Hg), and so on. As these metals are not biodegradable,
6
they tend to accumulate in the living organisms and lead to various diseases and
disorders which ultimately threaten human life. They can cause ill health, even when
present in the range of parts per billion (ppb) [5]. Biosorption has emerged as an
attractive option over conventional methods for the removal of heavy metal ions from
effluents discharged from various industries which ultimately reach and pollute fresh
water bodies. This chapter reports the toxicity of heavy metals, the advantages of
biosorption, various biosorbents used for the removal of metal ions, effect of
immobilization and modifications of biosorbents, various factors affecting the
process of biosorption, different bioreactors used in biosorption, and the application
of biosorption for the removal of metal ions from various wastewaters like industrial
effluents and contaminated water resources. The recent advances, current status, and
future of the process are discussed.

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2. Toxicity of heavy metals

Figure1: Heavy metals can damage living things

At low conc and tend to accumulate in the food chain

The pathway of exposure for heavy metals is mainly through inhalation, dermal
contact, and ingestion. The individual metal exhibits its own specific signs of toxicity
[6]. The severity of health effects is dependent on time and dose, the type of heavy
metal, and its chemical form. The nature of effect may be toxic, mutagenic,
neurotoxic, teratogenic, or carcinogenic [6]. Many studies reported that heavy metals
affect cell organelles and interact with cell components causing cell damage and
apoptosis. Even at a low level of exposure, they induce multiple organ damage.
Intoxication of heavy metals also leads to damage to the major systems in the body
and may lead to an increased risk in developing cancers [7]. Metal ion pollution is
highly persistent, and most of them are nonbiodegradable. The presence of various
heavy metals such as chromium (Cr), lead (Pb), zinc (Zn), arsenic (As), copper (Cu),
nickel (Ni), cobalt (Co), cadmium (Cd), and mercury (Hg) causes disturbances in
circulatory, gastrointestinal, and nervous systems. They also affect various organs
and lead to blindness, deafness, brain damage, loss of fertility, cancer, and many
other severe health problems.

8
 Figure 2 :types of heavy metals

3-Bioaccumulation and biosorption

In view of the disadvantages associated with conventional methods for metal

removal, there is a need for alternative, cost-effective technologies. In recent years,
biosorption/bioaccumulation processes have been considered as novel, economic,
efficient, and eco-friendly alternative treatment technologies for the removal of heavy
metals from contaminated wastewaters generated from various industries.

3.1. Bioaccumulation

Bioaccumulation is a metabolism-mediated active process in which the metal ions

accumulate the biosorbent intracellularly in the living cells. The process occurs in
two steps: the first step is the adsorption of metal ions onto cells, which is quick and
identical to biosorption, and the later step is slower which includes the transport of
metal species inside the cells by active transport [10] Unlike biosorption, it is an
irreversible, complex process which depends on the metabolism of the cells. The
process of bioaccumulation occurs by cultivating the biomass of a microorganism in
the vicinity of the metal to be accumulated. Since the solution contains the growth
medium, the organism begins its metabolic processes and activates the intracellular
transport systems for the accumulation of the sorbate. However, the major limitation
of the process is that the nutritive medium for growth of the microorganism contains
organic carbon sources [11, 12]. Bioaccumulation is an active process which requires
a living biosorbent and is mediated by the metabolism of the microorganism used.
The process operates by cultivating the microbe in the presence of a metal ion which
has to be removed. Part of the biosorbate accumulates inside the cell which enables

9
the biomass to increase and bind greater amounts of metal ions. The organisms which
are capable of resisting high loads of metal ions are best suited for accumulating
metal species. They do not possess any mechanisms for hindering the accumulation
of metal ions in large quantities [13]. They may possess special mechanisms for
synthesizing special intracellular binding regions rich in thiol groups as a response to
metal ions in their surviving environment. It was found that morphology and
physiology of the cell changes upon increase in concentration of the metal ion to be
accumulated [14]. Efficient bioaccumulation can be achieved by selecting the
microbes that are screened from polluted environments [15]. Pichia stipitis yeast was
capable of bio-accumulating Cu (II) and Cr (III) with the maximum uptake capacity
of 15.85 and 9.10 mg/g, respectively, from aqueous solutions with an initial
concentration of 100 ppm at pH 4.5 [16]]. Aspergillus niger was capable of removing
Cu (II) and Pb (II) with the maximum uptake capacity of 15.6 and 34.4 mg/g,
respectively [17]
Table:1 summarizes some more examples of biosorbents used for metal
bioaccumulation.

10
Since the process of bioaccumulation is achieved with the living organisms, the
uptake capacity was determined with the wet weight of the biosorbent.

3.2. Biosorption

Biosorption can be defined as a simple metabolically passive physicochemical

process involved in the binding of metals ions (biosorbate) to the surface of the
biosorbent which is of biological origin [18]. Biological removal includes the use of
microorganisms, plant-derived materials, agriculture or industrial wastes,
biopolymers, and so on. It is a reversible rapid process involved in binding of ions
onto the functional groups present on the surface of the biosorbent in aqueous
solutions by means of various interactions rather than oxidation through aerobic or
anaerobic metabolism [19]. The advantages of this process include are simple
operation, no additional nutrient requirement, low quantity of sludge generation, low
operational cost, high efficiency, regeneration of biosorbent, and no increase in the
chemical oxygen demand (COD) of water, which are otherwise the major limitations
for most of the conventional techniques [20].Biosorption can remove contaminants
even in dilute concentrations and has special relevance with respect to heavy metal
removal owing to toxicity at ppb levels. Microorganisms (live and dead) and other
industrial and agriculture byproducts can be used as biosorbents for the process of
biosorption.

The first stage in biosorption is that biosorbent should be suspended in the solution
containing the biosorbate (metal ions). After incubation for a particular time interval,
equilibrium is attained. At this stage, the metal-enriched biosorbent would be
separated [20]. The process of biosorption is advantageous because it is reversible,
does not require nutrients, a single-stage process, of quick range, has no danger of
toxic effects and cellular growth, allows intermediate equilibrium concentration of
metal ions, and is not controlled by metabolism [21].

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Biosorption capacity (mg/g) of the biosorbent can be defined as the amount of
biosorbate (metal ions) biosorbed per unit weight of the biosorbent and can be
expressed by using the following mass balance equation:

The percent biosorption (R%) known as biosorption efficiency for the metal was
evaluated from the following equation:

where qe is the amount of adsorbed metal ions of the adsorbent (mgg-1)

, Ci is the initial concentration of metal ion in the solution (mg L−1), Ce is the
equilibrium concentration of metal ion in the solution (mg L−1), V is the volume of
the medium (L), and m is the amount of the biomass used in the adsorption process
(g).

4-Mechanism of biosorption
The mechanism of biosorption is a complex process which involves the binding of
sorbate onto the biosorbent. Many natural materials can be used as biosorbents which
involve the binding of metal ions by physical (electrostatic interaction or van der
Waals forces) or chemical (displacement of either bound metal cations (ion
exchange) or protons) binding, chelation, reduction, precipitation, and complexation
(refer Figure1). Biosorbents contain chemical/functional groups like amine, amide,
imidazole, thioether, sulfonate, carbonyl, sulfhydryl, carboxyl, phosphodiester,
12
phenolic, imine, and phosphate groups that can attract and sequester metal ions. The
key factors controlling and characterizing these mechanisms are [22,23]:
 the chemical, stereochemical, and coordination characteristics of metal ions
like molecular weight, ionic radius, and oxidation state of the targeted metal
species;
 properties of the biosorbent, that is, the structure and nature (in case of
microorganism—living/non-living);
 type of the binding site (biological ligand)
 the process parameters like pH, temperature, concentration of sorbate and
sorbent, and other competing metal ions; and
 availability of the binding sites.

Figure 3: Biosorption mechanism

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The combined effects of the above parameters influence the metal speciation (the
formation of new forms of metal as a result of biosorption)

4.1 Complexation

It is defined as the formation of a complex by the association of two or more species.

Mononuclear (monodentate) complexes are formed between the metal ion and the
ligands in which the metal atom occupies the central position. Polynuclear
(multidenate) complex is formed by more than one metal ion in the center and the
metal atom may carry a positive, negative, or neutral charge depending on the
number of binding ligands involved. The complex formation to the monodentate
ligand is more preferable than multidentate because the latter contains multiple
ligands which may lead to multiple species binding. The metal ion interacts with the
ligands by covalent bonds. The attenuated total reflection infrared spectral (ATR-IR)
analysis of Cyanobacterium microcystisafter the biosorption of antimony (III)
suggested the involvement of carboxyl, hydroxyl, and amine groups through surface
complexation [24].
A similar mechanism of biosorption was reported by other studies by using
Acidiphilium, Termitomycesclypeatus, and alkali-modified sewage sludge for the
removal of Cd (II), Cr (VI), and Cd (II), respectively [25,26,27].

4.2 Chelation

It refers to the process in which a chelating agent binds to the metal ion at more than
one place at a time in order to form a ring structure and the complex is known as
chelate. Mostly polydentate ligands participate in the reaction to form stable
structures by multiple bonding. An increase in binding sites of the ligand increases
the stability of the structure. Chelates are more stable than complexes because of
multiple binding with the metal ion in more than one place. Rice straw was used as a
potential biosorbent for the removal of Cd (II) from the effluent. The biosorbed Cd
(II) chelates with the functional groups such as C=C, C–O, and O–H and carboxylic
acids which are present on the surface of the biosorbent [28]. A similar mechanism of
14
biosorption was reported in the removal of Cr (III) and Cu (II) by carboxyl and
hydroxyl groups present on the surface of soybean meal waste [29].

Figure 4: Chelation
4.3. Coordination
The metal atom in the complex is bound to its immediate neighbors by a coordinate
covalent bond by accepting a lone pair of electrons from the non-metal atom. The
non-metal atom is known as the donor (coordinating atom) and the metal atom which
accepts the electron pair is known as the acceptor. Compounds having such types of
bonds in their structure are known as coordinate compounds. Some examples of
coordinating groups are =O, –NH2, –NH, –N=, –OH, –S–, –O–R, and =NOH.

4.4. Ion exchange

Ion exchange is an important concept in biosorption which involves the exchange of

binary metal ions during biosorption with the counter-ions present on the surface of
the biosorbent. Most of the purification process works on the mechanism of ion
exchange. Ion exchange can take place either by cation or anion exchange. Carboxyl
groups can be a good example of cation exchangers while amino/imidazole groups
represent anion exchangers. The process of biosorption of Cr (III), Cd (II), and Cu
(II) by Spirulina was studied. Three functional groups capable of cation exchange
were identified on the surface: phosphate, carboxyl, and hydroxyl groups [30]. Ion
exchange mechanism of biosorption was reported in other studies using rice straw for
the removal of cadmium by exchange with K+, Na+, Mg+, and Ca+ and for the
removal of Cu (II), Zn (II), and Pb (II) using watermelon rind [28, 31

15
 Figure 5:Ion exchange for waste water treatment

4.5. Precipitation

The metal ions form precipitates with the functional groups present on the surface of
the microbial cells and remain intact or penetrate into the microbial cell. Most cases
involve the formation of insoluble inorganic metal precipitates. Organic metal
precipitates may be formed when microbial cells are used. Most of the extracellular
polymeric substances excreted by the microbes are involved in the formation of
organic precipitates. Precipitation of Cu (II) onto Mesorhizobiumamorphae causes
deformation, aggregation, and damage to the cell surface as shown by scanning
electron microscope-energy dispersive X-ray (SEM-EDX) analysis [32]. This
mechanism of precipitation for biosorption of metal ions was reported by other
studies using soybean meal, watermelon rind, and green tomato husk (Physalis
Philadelphia lam) for the removal of Cr (III) and Cu (II); Cu (II), Zn (II), and Pb (II);
and Fe and Mn, respectively [29, 31, 33]. addition of chemicals to alter the physical
state of dissolved and suspended solids and facilitate their removal by sedimentation.

Figure6::precipitation for waste water treatment

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4.6. Reduction

In this process, the metal interacts with the functional groups like carboxyl, gets
reduced, and leads to the growth of crystals. Elements like gold and palladium have
been obtained by the process of reduction. The metal gets reduced once it binds to the
biosorbent at discrete places. Removal of toxic hexavalent chromium can be done by
the process of reduction. Many organisms remove Cr (VI) by reduction to Cr (III) by
biosorption from the aqueous solution [34, 35, 36].

The mechanism of biosorption can be studied using different techniques. The acidic
and basic properties of the functional groups that are present on the material surface
and ion exchange properties can be determined by Boehm method or potentiometric
titration [37]. Fourier transform infrared spectrometry (FTIR) offers important
information about the functional groups that are present on the surface of biosorbents
like carboxyl, amino, amide, hydroxyl, sulfate, carbonyl, ether, ester, and the nature
of the bond that are involved in biosorption [38]. Scanning electron microscope
(SEM) is a powerful technique for qualitative evaluation of the structure and
morphological changes of the biosorbent before and after metal biosorption. Energy
dispersive X-ray (EDX) technique provides valuable information about the
availability of various elements on the surface of the biosorbent. X-ray photoelectron
spectroscopy (XPS) is a quantitative spectroscopic technique for analyzing the
surface chemistry of the biosorbent, that is, electronic state and empirical formula of
the elements present and oxidative state of the biosorbed metal ion [39].

5.Advantages and Disadvantages of Biosorbtion

•Advantages:

1) Growth-independent, non-living biomass is not subject to toxicity limitation of

cells. No requirement of costly nutrients required for the growth of cells in feed

17
 solutions Therefore, the problems of disposal of surplus nutrients or metabolic
products are not present.
2) Biomass can be procured from the existing fermentation industries, which is
essentially a waste after fermentation.
3) The process is not governed by the physiological constraint of living microbial
cells.
4) Because of non-living biomass behave as an ion exchanger; the process is very
rapid and takes place between few minutes to few hours. Metal loading on
biomass is often very high, leading to very efficient metal uptake.
5) Because cells are non-living, processing conditions are not restricted to those
conducive for the growth of cells. In other words, a wider range of operating
conditions such as pH, temperature and metal concentration is possible. No
aseptic conditions are required for this process. Metal can be desorbed readily
and then recovered if the value and amount of metal recovered are significant

•Disadvantages:

1) Early saturation can be problem i.e. when metal interactive sites are occupied,
metal desorption is necessary prior to further use, irrespective of the metal
value.
2) The potential for biological process improvement (e.g. through genetic
engineering of cells) is limited because cells are not metabolizing. Because
production of the adsorptive agent occurs during pre-growth, there is no
biological control over characteristic of biosorbent. This will be particularly
true if waste biomass from a fermentation unit is being utilized.
3) There is no potential for biologically altering the metalvalency state.
For example less soluble forms or even for degradation of organometallic
complexes [40]

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 Chapter 2
"Exploring Factors in Batch Biosorption Experiments"

6. Batch experimental

Figure 7: batch experiment system

A biosorption process can be performed via several modes; of which, batch and
continuous modes of operation are frequently employed to conduct laboratory scale
biosorption processes. Although most industrial applications prefer a continuous
mode of operation, batch experiments have to be used to evaluate the required
fundamental information, such as biosorbent efficiency, optimum experimental
conditions, biosorption rate and possibility of biomass regeneration, batch system.

6.1:Factors influencing batch biosorption

The important factors include: solution pH, temperature, ionic strength, biosorbent
dosage, biosorbent size, initial solute concentration, agitation rate. Of these, the
solution pH usually plays a major role in biosorption, and seems to affect the solution
chemistry of metals/ dyes and the activity of the functional groups of the biomass
[1].

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6.1.1Effect of pH

It has been shown that the affinity of cationic species for the functional groups
presents on the cellular surface is strongly dependent on the pH of the solution. The
biosorpitive capacity low at low pH values and increases with pH until reaching an
optimum pH , However at pH higher than metals begins to precipitate due to
formation of M(OH). At low pH values, cell wall ligands are closely associated with
hydronium ions and restrict the bisorption of mn+ as a result of competition
betweenH₃O⁺ and mn+ with the bacterial biosorbent cell wall ligands. As the pH
increases, more ligands, such as carboxyl, phosphate, imidazole, and amino groups,
would be exposed and carry negative charges which attract mn+ and biosorb it onto
the cell surface [42].

6.1.2Effect of temperature

If temperature increasing, it usually enhances biosorptive removal of adsorptive

pollutant by increasing surface activity and kinetic energy of the adsorbate, but may
damage physical structure of biosorbent [43].

6.1.3Effect of Ionic strength

If ionic strength increasing, it reduces biosorption removal of adsorptive pollutant by

competing with the adsorbate for binding sites of biosorbent.

6.1.4. Effect of initial pollutant concentration

If initial pollutant concentration increasing, it increases the quantity of biosorbed

pollutant per unit weight of biosorbent, but decreases its removal efficiency [43].

6.1.5. Effect of biosorbent dosage

The dosage of a biosorbent strongly influences the extent of biosorption. In many

instances, lower biosorbent dosages yield higher uptakes. An increaseing the biomass

20
concentration generally increases the amount of solute biosorbed, due to the
increased surface area of the biosorbent, which in turn increases the number of
binding sites conversely, the quantity of biosorbed solute per unit weight of
biosorbent decrease with increasing biosorbent dosage, which may be due to the
complex interaction of several factors. An important factor at high sorbent dosages is
that the available solute is insufficient to completely cover the available exchangeable
sites on the biosorbent, usually resulting in low solute uptake . Also, as suggested by,
the interference between binding sites due to increased biosorbent dosages cannot be
over ruled, as this will result in a low specific uptake [44].

6.1.6 Effect of biosorbent size

If biosorbent size decrease, it is favorable for batch process due to higher surface area
of the biosorbent, but not for column process due to its low mechanical strength and
clogging of the column [43].

6.1.7 Effect of agitation speed

If agitation speed increasing, it enhances biosorptive removal rate of adsorptive

pollutant by minimizing its mass transfer resistance, but may damage physical
structure of biosorbent [43].

6.1.8 Effect of Other pollutant concentration.

If coexisting pollutant competes with a target pollutant for binding sites or forms any
complex with it, higher concentration of other pollutant will reduce biosorptive
removal of the target pollutant [43].

7. A comparison between different biosorbents.

Identification of biosorbents for the process of biosorption is a majorchallenge. It is
desirable to develop/obtain biosorbents with thecapacity to bind/uptake metal ions
with greater affinities [56]. A widevariety of materials available in nature can be used
21
as biosorbents forthe removal of metals from contaminated water resources. Any
kindof plant, animal, and microbial biomass and their derivatives; plant,industrial and
agriculture wastes; and byproducts discharged fromvarious industries can be
employed as biosorbents. It is important toselect a biosorbent from the large spectrum
of available materials.The desired characteristics of an ideal biosorbent are [56]:
 high affinity for metals (biosorption capacity)
 low economic values (low cost)
 availability in large quantities
 easy desorption of the adsorbed metal ions and possible multiple
reuse of the biosorbentThe use of different materials as biosorbents is explained in
detail:

a) Algae:

New biosorbent materials has focused especially on algae, due to its high sorption
capacity and its availability in almost unlimited amounts. They are divided into
several evolutionary pathways completely independent: a red pathway with red algae
(Rhodophyta), a brown pathway with brown algae (inter alia, Chromophyta) and a
green pathway that includes green algae (Chlorophyta). Differences between these
types of algae are mainly in the cell wall, where sorption takes place. Research in the
field of biosorption has mostly concerned itself with brown algae, the cell walls of
brown algae generally contain three components: cellulose, the structural support;
alginic acid, a polymer of mannuronic and guluronic acids and the corresponding
salts of sodium, potassium, magnesium and calcium; and sulphated polysaccharides.
As a consequence, carboxyl and sulphate are the predominant active groups in this
kind of algae [45].The carboxylic groups are generally the most abundant acidic
functional group in the brown algae. They constitute the highest percentage of titrate
blesites(typically greater than 70%) in dried brown algal biomass. The adsorption
capacity of the algae is directly related to the presence of these sites on the alginate

22
polymer, which itself comprises a significant component (up to 40% of the dry
weight, of the dried seaweed biomass) [46].

Figure 8. Algae biosorbents heavy metals

b) Bacteria:

Bacteria are a major group of unicellular living organisms belonging to the

prokaryotes, which are ubiquitous in soil and water, and as symbionts of other
organisms. Bacteria can be found in a wide variety of shapes, which include cocci
(such as Streptococcus), rods (such as Bacillus), spiral (such as Rhodospirillum) and
filamentous (such as Sphaerotilus). Eubacteria have a relatively simple cell structure,
which lack cell nuclei, but possess cell walls . The bacterial cell wall provides
structural integrity to the cell, but differs from that of all other organisms due to the
presence of peptidoglycan (poly- N-acetylglucosamine and N-acetylmuramic acid),
which is located immediately outside of the cytoplasmic membrane. Peptidoglycan is
responsible for the rigidity of the bacterial cell wall, and determines the cell shape.

Mechanism of bacterial biosorption:

The bacterial cell wall is the first component that comes into contact with metal
ions/dyes, where the solutes can be deposited on the surface or within the cell wall
structure. Since the mode of solute uptake by dead/inactive cells is extracellular, the
chemical functional groups of the cell wall play vital roles in biosorption. Due to the
nature of the cellular components, several functional groups are present on the
bacterial cell wall, including carboxyl, phosphonate, amine and hydroxyl groups[41].
23
c) fungi

Fungal cell walls and their components have a major role in biosorption and also take
up suspended metal particulates and colloids. Fungi are ubiquitous in natural
environments and important industrial processes. Their most important roles are as
decomposers of organic material, with concomitant nutrient cycling as pathogens and
symbiotic with animals and plants, and as spoilage organisms of natural and synthetic
materials [47]. White rot fungi are highly specialized groups of organisms. They are
Basidomycetes, which include all the higher fungi that are characterized by their
sexual fruiting bodies [48]. Lentinussajor-cajuis a wellknown white rot, fungus
whereas a little attention has been paid to the ability of its potential for the removal of
mixed pollutants from environment [49]

Figure 9: Biosorption mechanisms of copper, cobalt and other heavy metals by filamentous fungi

d) cultural waste

cultural waste and other agricultural by-products such as sugarcane bagasse, soya
bean hulls, walnut hulls , cotton seed hulls and corn cobs.[50].carrot residues , used
for biosorption because there are readily available, for example carrot residues was
used as a biosorbent for the removal of heavy metals. The cation exchange properties
of these residues can be attributed to the presence of carboxylic and phenolic
24
functional groups, which exist in either the cellulosic matrix or in the materials
associated with cellulose, such as hemicellulose and lignin [51].

8. Desorption and the regeneration of biosorbents

In order to keep the process costs down and for recovery of valuable metal ions after
the biosorption, it is crucial for regeneration of the biosorbent [52]. The primary
objective of desorption is to retain the adsorption capacity of the biosorbent. The
process of desorption should be such that the metal can be recovered in the
concentrated form (in case of metals of economic value), and the biosorbent needs be
restored to the original state with undiminished biosorption capacity for reuse [8]
Hence an appropriate eluent for desorption should meet the following requirements
[53]
 low cost;
 environment friendly;
 non-damaging to the biomass; and
 ensure intact metal-binding capacity.
The possible eluents are dilute mineral acids (HCl, H2SO4 and HNO3), organic acids
(citric, acetic and lactic acids), and complexing agents (EDTA, thiosulphate, etc.) for
the recovery of the biosorbent and metal recovery. Desorption efficiency can be
determined by the S/L ratio, that is, solid to liquid ratio. The solid represents the
biosorbent and liquid represents the eluent (volume) applied. For complete elution
and to make the process economical, high S/L values are desirable [3]. Although,
desorption is considered advantageous, in some instances, a loss in the capacity of the
biosorbent to retain the desired metal ion has been reported. The metal Cr (VI) was
desorbed almost completely from the Mucor hiemalis biomass by using 0.1 N of
NaOH. The biomass retained its activity of biosorption and desorption up to five
cycles. Experimental data fit well with the Langmuir isotherm model, and FTIR
analysis showed that the amino groups are involved in biosorption [54] Table2

25
summarizes the use of different eluents for the desorption of metal ions from different
biosorbents.

Table 2. Use of different eluents for desorption of metal ions.

26
9-Experimental methods and techniques
1. Batch Equilibrium Studies: This involves mixing a known quantity of
biosorbent material with a solution containing the pollutant for a specific
period. After equilibrium is reached, the concentration of the pollutant in the
solution is measured to determine the extent of biosorption.
2. Column Studies: In this method, the polluted solution is passed through a
column packed with biosorbent material. The column parameters such as flow
rate, bed height, and initial concentration of the pollutant are controlled to
study the biosorption efficiency under dynamic conditions.
3. Kinetic Studies: Kinetic studies investigate the rate at which biosorption
occurs. This involves monitoring the decrease in pollutant concentration over
time to determine the rate of biosorption and to understand the underlying
mechanisms.
4. Isotherm Studies: Isotherm studies provide information on the relationship
between the equilibrium concentration of the pollutant on the biosorbent
material and the concentration of the pollutant in the solution at equilibrium.
Common models used include Langmuir, Freundlich, and Temkin isotherms.
5. Characterization Techniques: Various analytical techniques are used to
characterize the biosorbent material before and after biosorption. These
include scanning electron microscopy (SEM), Fourier-transform infrared
spectroscopy (FTIR), X-ray diffraction (XRD), and surface area analysis
(BET).
6. Optimization Studies: Optimization studies involve varying parameters such
as pH, temperature, biosorbent dosage, and contact time to maximize
biosorption efficiency.
7. Desorption Studies:Desorption studies involve the removal of the pollutant
from the biosorbent material after biosorption has occurred. This helps in
understanding the reversibility of the process and the potential for
regeneration of the biosorbent material for reuse.

27
 8. Mathematical Modeling: Mathematical models are often developed to
describe the biosorption process quantitatively and to predict biosorption
behavior under different conditions.

10..Biosorption equilibrium isotherms

Sorption isotherms explain the equilibrium relationships between biosorbent and

biosorbate and the mass of the biosorbed component per unit mass of biosorbent and
the concentration of biosorbate in the medium under a given set of conditions
(temperature and concentration). It also determines the equilibrium distribution of
metal ions and how selective retention takes place when two or more biosorbent
components are present [55]. The term ―isotherm‖ can be defined as a curve
explaining the retention of a substance on a solid at various concentrations [56]. The
determination of equilibrium parameters is the basic requirement for designing a
good biosorption system. For determination of the best-fitting sorption isotherm,
linear regression is frequently used. In order to predict the isotherm parameters, the
method of least squares is applied.
The biosorption capacities of different biosorbents for different pollutants can be best
explained by biosorption equilibrium isotherms. Several isotherm models are
available to describe the mechanism of the biosorption process and the equilibrium
biosorption distribution. Some of the isotherms used in biosorption studies are
Langmuir, Freundlich, and Temkin isotherms. However, the biosortion process may
show better fit with a specific isotherm.
Biosorption isotherm data of Pb (II) and Cu (II) ions onto green algal species,
Spirogyra and Cladophora, were in good agreement with the Langmuir isotherm
demonstrating the formation of the monolayer coverage of metal ions on the outer
surface of the biosorbent [57]. The Langmuir model fitted well with the biosorption
of Pb (II), Zn (II), and Ni (II) ions onto Bacillus subtilis [58]. Freundlich isotherm
showed the best fit for the biosorption of Cu (II) ions onto lactic acid bacterium,

28
Enterococcus faecium [59]. Biosorption of Cr (VI) ions onto Bacillus thuringiensis
also shows the better fit with Freundlich isotherm [60].

11.Bioreactors used for biosorption

Various types of bioreactors have been investigated for application at the industrial
level. A bioreactor is a system used for the production of microorganisms or desired
metabolites employing defined and controllable factors. The typical categories of
bioreactors used for the biosorption are stirred tank bioreactors (STRs), air lift
bioreactors (ALRs), fluidized bed bioreactors (FBRs), and fixed bed bioreactors
(FXRs). These reactors can be operated either in batches or in continuous modes or
both (fixed bed and stirred tank bioreactors). Factors (pH, temperature, mixing and
agitation, and nutrient availability) affecting the process of biosorption in the
bioreactor have to be optimized and controlled by using cooling jackets
(temperature), baffles/agitators (mixing), feed lines (supplies nutrients), and acid/base
addition (pH) [61].

29
 Chapter 3
" Biosorption in Industry : Present and Future"

12.Industrial Applications

1. Mining and Metallurgical Industries: Mining activities often result in the

release of heavy metals into wastewater. Biosorption processes have been
studied and implemented in mining industries to treat effluents contaminated
with metals such as copper, zinc, lead, and cadmium. Biosorbents derived from
agricultural waste, microbial biomass, and algal biomass have shown promise
in removing these metals effectively.
2. Electroplating and Surface Finishing Industries: Electroplating and surface
finishing operations generate wastewater containing high concentrations of
heavy metals like chromium, nickel, and copper. Biosorption techniques have
been explored as a cost-effective and environmentally friendly alternative for
treating these effluents. Biosorbents such as activated carbon, algae, and
bacterial biomass have been investigated for their efficacy in removing heavy
metals from electroplating wastewater.
3. Textile and Leather Industries:Textile dyeing and leather tanning processes
involve the use of heavy metal-containing dyes and chemicals, leading to
wastewater pollution. Biosorption methods have been employed to treat
effluents from these industries, with biosorbents such as fungi, bacteria, and
agricultural waste materials effectively removing heavy metals from dyeing
and tanning wastewater.
4. Municipal Wastewater Treatment Plants: Municipal wastewater treatment
plants face challenges in removing heavy metals present in industrial and
domestic wastewater streams. Biosorption technologies have been integrated
into existing treatment systems to enhance heavy metal removal efficiency.
Studies have demonstrated the use of biosorbents like algae, bacteria, and

30
 activated carbon in municipal wastewater treatment for effective metal
removal.
5. Environmental Remediation Projects: Biosorption techniques have been
applied in environmental remediation projects to clean up contaminated sites
and water bodies. Biosorbents such as peat moss, agricultural waste, and
microbial biomass have been used to remove heavy metals from soil and water,
helping restore ecosystems and protect human health.

These industrial applications and studies highlight the versatility and effectiveness of
biosorption as a sustainable approach for heavy metal removal from wastewater,
contributing to environmental protection and resource conservation efforts. Ongoing
research continues to explore new biosorbents, optimization strategies, and scale-up
techniques to further enhance the efficiency and feasibility of biosorption processes
in various industrial sectors.

13-Commercialization and adoption of biosorption as waste

treatment technology

In spite of the advantages over other conventional techniques, there is a glaring lack
of adoption of biosorption as a waste treatment technology. Few commercial ventures
offering biosorption as a treatment have emerged. A few commercial biosorbents are
available . There is a dearth of field trials for a seemingly promising decade-old
technology.
Volesky and Naja reported that the lack of commercialization was due to non-
technical reasons—due to lack of partners. Computer models based on pilot tests can
reduce the scope of field tests. Data and cases of application can attract investors,
consultants, distributors, and clients .
The BV Biosorbex Inc. is a Canadian company, started by Professor Bohumil
Volesky of McGill University, Montreal, Canada, involved in commercializing
biosorption. Its services include the biosorption-based removal of heavy metals from

31
industry waters using reactors carrying novel biosorbents as granules offered at the
1/10th the cost of ion exchange resins. The biosorbents may be made from industrial
waste, algal biomass, and specialized biomass. The biosorbents are reported to
function between pH 4–10 and 5–75°C with efficiencies of >99.9% at 10–50 ppb
concentrations of heavy metal and organic matter (<5000 mg/L). The company can
conduct lab-scale studies, consultancy, design process, and operate waste treatment
plants. Pilot biosorption systems may involve column, fluidized bed, or mixed tank
reactors. The company plans to capture 15% of market of ion exchange resin

14-Future perspectives and research directions for adsorption of

heavy metals from wastewater

1. Development of Novel Adsorbent Materials; Research efforts aim to explore

and develop new adsorbent materials with enhanced adsorption capacities,
selectivity, and stability. This includes the synthesis of advanced
nanomaterials, functionalized polymers, bio-based adsorbents, and hybrid
composites tailored for specific heavy metal removal applications.

2. Understanding Adsorption Mechanisms: Future research aims to deepen our

understanding of the fundamental adsorption mechanisms governing heavy
metal adsorption onto various adsorbents. This includes elucidating the roles of
surface chemistry, pore structure, and interfacial interactions in determining
adsorption performance, as well as investigating kinetic and thermodynamic
aspects of adsorption processes.

3. Optimization of Process Parameters: Research focuses on optimizing process

parameters such as pH, temperature, contact time, adsorbent dosage, and flow
rate to maximize adsorption efficiency and minimize operational costs.
Advanced modeling and simulation techniques can aid in the design and
optimization of adsorption systems for real-world applications.

32
4. Integration of Adsorption with Other Treatment Processes:Future research
seeks to explore synergistic approaches by integrating adsorption with other
wastewater treatment processes such as coagulation, precipitation, membrane
filtration, and biological treatment. Combined treatment strategies can enhance
overall treatment efficiency, reduce treatment costs, and address complex
wastewater compositions more effectively.

5. Regeneration and Reuse of Adsorbents: Efforts are directed towards

developing sustainable regeneration methods for spent adsorbents to extend
their lifecycle and minimize waste generation. This includes exploring
environmentally friendly regeneration techniques such as chemical desorption,
thermal regeneration, and biological regeneration, as well as investigating
strategies for reusing regenerated adsorbents.

6. Scale-up and Commercialization:Future research aims to bridge the gap

between laboratory-scale studies and full-scale implementation by addressing
scale-up challenges and demonstrating the feasibility of adsorption
technologies for industrial applications. This includes conducting pilot-scale
studies, assessing the scalability of adsorption processes, and evaluating the
techno-economic viability of large-scale implementation.

7. Environmental and Health Impacts Assessment: Research efforts focus on

assessing the environmental and health impacts of adsorption-based treatment
technologies, including the fate and transport of adsorbents and adsorbed
contaminants in the environment. This includes conducting life cycle
assessments, risk assessments, and toxicity studies to ensure the sustainability
and safety of adsorption processes.

33
 Conclusions

One advantage of biosorption is the removal of residual or minute concentrations of

contaminants. Conventional water treatments may not completely remove
contaminants. Hence, biosorption may be integrated downstream of other
conventional water treatments. This is especially relevant in the case of pollutants
like heavy metals whose effects are felt even at ppb levels.

The efficiency for the removal of specific metals is hindered by the presence of other
contaminants. This may be important during the recovery of specific metals of
economic value. In this regard, biosorption may be applied to wastes and effluents
before it enters the sewage or natural discharge streams like rivers, seas and so on.

However, with the aim of treating effluent/remediating water resources of all/most

contaminants, it may be an advantage to have all pollutants (metal or contaminants)
removed simultaneously using a non-specific/non-selective biosorbent and reducing
the number of operations/steps. Multiple biosorbents of different
specificities/selectivities can also be used.

The strains or biomass used as the biosorbent should be of safe origin especially for
water treated for human or animal consumption. Hence, pathogens and toxin-
producing organisms need to be avoided. In this regard biomass from food-grade
microorganisms like lactic acid bacteria and (wine/beer yeast) and agro-waste is of
significance.

Regeneration and immobilization of biomass in order to reduce the cost of biomass

involve the use of hazardous solvents which can lead to pollution. Hence, the use of
harmless chemicals may be explored.

34
The existing waste can be classified as solid (degradable and non-degradable) and
liquid in nature. A lot of solid non-biodegradable wastes (plastic) can be recycled to
form chemically and mechanically robust and inert matrices to hold the biosorbent.
Degradable wastes or biomass (agricultural/domestic/industrial) can be employed as
biosorbents. A compatible biosorbent-matrix combination can then be employed to
treat liquid discharge/effluents. This can make the waste treatment economical and
sustainable while addressing the problems of solid and liquid effluents
simultaneously.

Nature provides a diversity of biomass varying in binding specificity, efficiency, and

ruggedness. This diversity can be tailored to site-specific waste treatment needs by
applying the advanced techniques of recombinant DNA technology, synthetic biology
and so on. Strains can be modified to express single/multiple metal-binding proteins
on the cell surface. Chimeric proteins with multiple metal-binding domains having
suitable binding and regeneration conditions can be engineered and expressed.
Binding and regeneration conditions for the biosorbents can also be manipulated.
Strains tolerant to harsh waste environments, and/or able to accumulate the toxic
metals can be developed. However, laws regulating the dispersal or
release/containment of genetically modified organisms will need to be considered.
Techniques like genome shuffling are considered natural and can be employed for the
modification of microorganisms. Confusion exists on the Crispr–Cas9 technology if it
can be considered a genetic modification. Also, biosorption processes involving dead
biomass may be a convincing argument against such regulations.

Nanotechnology is a cutting-edge technology involving the development of novel

materials through the manipulation at nanoscale. The use of biomass has been
explored to produce nanometal particles of silver, Cu, gold and so on. This novel use
of biosorption linking the wastewater treatment to synthesis/the recovery of
metals/nanometals from wastewater makes economic sense for capital investment.

35
The development of novel efficient biosorbents (nanocellulose, nanocomposites like
pectin/TiO2, nano Fe3O4/Sphaerotilusnatans, ostrich bone waste-zero valent iron,
polyaniline-modified nanocellulose) has also been obtained by varied treatments
including solvents, heat, and so on. This may be the answer to optimizing and
economizing biosortion-based waste treatment by improving stable efficient
biosorbents.

Biosorbents carrying metals can be included into feeds or fertilizers as metals bound
to organic ligands have greater bioavailability. Also, they can enhance the shelf life
of the feed involved.

However, biomass may also bind hazardous chemicals (like dyes) when used with
industrial effluents. The use of such biomass into feeds is not recommended.

Biosorption is beneficial over conventional techniques. The potential has been

demonstrated at laboratory and pilot scales even with actual effluent/discharges. But
there is a dearth of examples in the real scenario at organized levels like
municipalities/cities/pollution treatment centers/industries. Few commercial ventures
have been made. This might be because of the diversity of pollutants and their
chemical and biological waste background. A set of promising biosorbents/processes
may need to be optimized or standardized for specific effluent types. The cost and
feasibility in terms of large-scale applications may be evaluated.

Routine adoption at municipal and industrial levels requires success stories at field
studies. Better metal removal efficiencies at lower costs and labor when compared to
other conventional treatments can convince the industry/state to adopt biosorption.
However, there is a lack of field experiments. Executing field studies needs great
coordination, capital, manpower, and infrastructure.

36
State intervention is needed to assist the scientific community to not only fund and
coordinate such large studies in terms of manpower/infrastructure but to also access
the industry(s) concerned. The general indifference of the industry toward waste
treatment may be an issue.

The state can act as bridge for informing and facilitating the availability of biomass
from different sources to different polluting units. Such efforts will create a mutually
sustainable waste treatment scenario. For example, the disposal of agro-waste from
the rural setup to polluting units in order to treat effluents is a win-win for both
parties.

An environment encouraging start-ups based on biosorption technology needs to be

created. Stringent norms and scrutiny against effluent discharge can convince the
industry to view waste treatment as a necessary investment rather than an avoidable
overhead cost. Under this scenario start-ups like Biosorbex, investing in eco-friendly
waste treatment technologies, can flourish.

Efforts may be devoted to also apply biosorption at domestic (household) or

community levels rather than awaiting the installation of large centralized water
treatment setups.

Techniques like response surface methodology, artificial neural networking, boosted

regression tree, and genetic algorithm may be used for process optimization.
Modeling should be done in solutions with multiple metals and organic matter
simulating the real wastewater conditions. Pilot and field studies should be conducted
comparing biosorption with the conventional techniques. The use of computer-based
simulations or modeling can reduce the number of field trials >

37
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