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INTRODUCTION
Biosorption is a physiochemical process involves the physical attachment of the chemical
species, is blessing for current age. In the way to progress many threats has been created by
man due to such threats survival of the mankind in future is the biggest unresolved mystery for
future. For better survival scientist are trying to clear all mess, heavy metals pollution is major
one of them. For economic reasons certain biomass materials help in absorption of various
waste materials as Biosorption is an intracellular process occur by passive absorption of waste
material in intracellular voids of biomass.
Metallic species persist in environment thus posing serious threat for mankind as they are
mainly discharged by industrial discharging activities , by their mobilization they enter into food
chain and are responsible for many disorders[1].Biosorption is a biological process, it is the
capability of biological species to attach heavy metals metabolically through passive uptake. By
using this heavy metals from environment can be clean up through eco-friendly way [2].
This technique is helpful for removal of nasty substances which are not easily biodegradable for
example dyes and heavy metals. It also provide basis for the removal of pollutants from worthy
resources of water which are necessary for survival of mankind. For the sake of its importance
this technique becomes necessary part of all environmental sciences. By using this technique
with the help of biomass environmental cleanup can be done. This process is easy to manage
and cheaper as well to being economically feasible. As it pose no negative effect on
environment i.e. Ecofriendly. The main advantage of using biomass as cleaning agent, which is
the main tool of this process is their efficiency and they can be used again and again.
1.1 Biomaterials:
A variety of biomaterials are available for Biosorption for example algae , fungi, bacteria etc.
which can readily bind with non-biodegradable materials such as heavy metals due to their
elastic nature of cell wall[3]. As peptidoglycan complex polysaccharide having various sugar
units in it , is present in cell wall is responsible for their elastic nature and is having affinity
toward heavy metal ions .Peptidoglycan is having carbonyl and alcoholic functional group in its
structure. Due to their presence this molecule possesses special attraction for heavy metallic
ions, dyes and various other pollutants. Because of this affinity heavy metallic ions get easily
attached with the internal environment of biomass thus easily removed from polluted water
reservoirs. This binding is physical one and can be easily reverse after the completion of process
that biomass is again ready to use.
1
In many cases immobilization of reactants is necessary to get maximum contact between
biomass and desired waste which we want to eliminate from reaction vessel. While some time
mobilization is done by using flask shaker or by magnetic stirrer. After this reaction medium is
analyzed till all metal or dye is consumed by biomass then for recovery of biomass for further
use recover processes are performed. Biomass for this valuable process is most preferably dead
plants parts due to remarkable abilities of cell wall, bacteria, fungus and algae can also be used
[4].
Fig 1: Structure of peptidoglycan in plant cell wall having –OH Network [5].
Biosorption was mainly use for the treatment of waste water, sewage and especially for
renovation of water from industrial effluent and uranium recovery. Now days this technique
become alternative option for dealing with waste water collected from chemical industries. It is
a simulation tool which involves both equilibrium and dynamic aspects of sorption. The basis of
this process came into being existence due to devastating effects of toxic metals and organic
pollutants .Once these heavy metals get enter into aquatic reservoirs through industrial
effluents
2
they move along the flow of water. As plants consume such water these metals get enter into
plant body which are ultimately consumed by human .Polluted water is discharged in to
drinkable sources of water reservoirs so, they are very important for life survival. So this
technique was initially use for the treatment of sewage ,drained wasted water as it must not
use for drinking purpose but can be utilized in other ways such as agricultural purposes just
after its processing in which it is passed through different stages for detoxification[7].
3
(precipitant) ultimately converted into water insoluble carbonates, sulphide and sulphates
more commonly. Which are separated by using sedimentation, centrifuge and filtration.
1.5.4 Ultrafiltration
This is an advance form of membrane filtration. By using pore size 0.1 to 0.001 µ ultrafiltration
can be achieved. This pore size not only allows water molecules to pass through it but also help
to retain large molecule such as macromolecules, colloids and heavy metals. By using polymer
efficiency of process can be up to 98.9 %.
1.5.5 Microfiltration
This technique is based on same principle as ultrafiltration works .The only difference among
these are the rejected larger pieces by ultrafiltration are removed by microfiltration as it utilize
filtration media having size smaller than ultrafiltration. By using cross flow microfiltration
technique is based on yeast based bioaccumulation typically for the removal of lead and
chromium.
1 Copper 0.421
2 Chromium 0.211
3 Lead 0.147
5
4 Cadmium 0.097
1.7.1 Bioaccumulation
Bioaccumulation is a kind of modified Biosorption which involve active participation of biomass.
In This process heavy metals are incorporated in intracellular parts of biomass by the aid of
metabolism.This irreversible and complex process which entirely depend upon metabolism of
cell. Basically in this process microbes are grown in vicinity of heavy metal ions to be
accumulated. Since the solution is having growth medium along with heavy metallic ions. As
microbes metabolize growth medium actively heavy metals also incorporated inside the cells.
6
1.7.1.1 Steps
This process is completed in two steps given below:
1. Adsorption of heavy metals on the surface of cell which is quick and similar as Biosorption.
2. Transport of heavy metals inside the cell by active transport which is time consuming step.
5 Bacillus Cr (lV) 32
megaterium
1.7.2.1 Advantages
This process is having many advantages given below:
1. Simple operation.
2. Low quantity sludge generation.
3. No additional nutrients supply is needed.
4. High efficiency.
5. Low operational cost.
6. Regeneration of biosorbents.
7. No increase in COD of water.
8. Reversible
9. No toxic effect on cellular growth.
10. Not controlled by metabolism of biomass.
11. Quick and fast result giver.
1.7.2.2 Stages
This process is begins with suspending the biosorbent in the solution containing biosorbate
which are heavy metals. After a certain time interval when equilibrium is reached at this stage
metal enriched biosorbent is removed from solution. This process is very useful as it is quick and
gives fruitful results.
8
Ci is the initial concentration of heavy metal (mg / L)
1.11.1 Complexation
In this process a mononuclear complex is formed between metal ion and biosorbent material
which behave as a ligand. Sometime polydentate ligand lead to the formation of polynuclear
complex in which poly dentate ligand is attaché by metallic ion on various sites as metal ion is
carrying positive charge and due to presence of electronegative ion and excess of electrons
9
make it negatively charge. More preferably mononuclear complexes are formed rather
than
10
polynuclear ligands. Because in polynuclear complex polydentate ligand and metal ion
interaction produce multiple binding through covalent bonding.Cyanobacterium microcytis on
Biosorption with antimony(lll) form similar kind of interaction due to presence of carboxyl,
hydroxyl and amine group through surface Complexation.
1.11.2 Chelation
In this process metallic ion interact with polydentate ligand through many sites result in
formation of ring structure which is more stable than ordinary complex. Increase in binding site
result in increase in stability of ring structure. Rice straw was used for the removal of cadmium
(ll) from industrial discharge. As rice straw is having hydroxyl O-H and carboxyl –COOH and
alkene C=C functional groups which are responsible for the attachment of metal ion with ligand
and due to stronger force of attraction lead to stable chelate. Soya bean also show similar kind
of interaction lead to chelate formation.
1.11.3 Coordination
This is a kind of interaction in which metal atom bind with neighboring atom through
coordinate covalent bond by accepting a pair of lone pair from neighboring nonmetallic atom.
The nonmetallic atom is donor and metallic partner is acceptor and such compounds are called
coordinate compounds. Some of coordinating groups are =O, - NH2 ,-NH , -OH etc.
1.11.5 Precipitation
Metals cations form insoluble precipitates with many inorganic reagents readily. Metallic
cations form insoluble precipitates with the functional groups which are present on the surface
of microbial or fungal biomass most of extracellular polymeric products are harvested by
microbes which are involved in the formation of organic precipitate .Cu(ll) precipitation can be
done by using Mesorhizobium amorphae as a result of that it cause aggregation, damage to cell
and deformation of the cell which can be studied by using scanning electron microscope-
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energy
12
dispersive x-ray(SEM-EDX). These mechanism of precipitation can be studied for by using
soybean meal, green tomato husk and watermelon rind for the removal of Cr (lll), Cu (ll); Cu(ll),
Zn(ll) and Pb(ll); Fe and Mn, respectively.
1.11.6 Reduction
This is the process which utilizes functional groups like carboxylic group which interact with
metal and result in reduction metal and lead to growth of crystal. Precious metal like gold and
palladium are harvested by this method. As metal bind with biosorbent by accepting electrons it
get reduced. By using this method we can get rid of toxic Cr (VI) to reduction to Cr (lll) from
aqueous solution. This process can utilize both acidic and basic medium. Fourier transform
infrared spectrometry(FTIR) provide us important information regarding functional groups
present on the surface of biosorbent like amide,amino,sulphate,ether, ester and nature of bond
which are modified in biosorption.X-ray photoelectron spectroscopy(XPS)is a quantitate
technique for analyzing surface chemistry of biosorbent include study of both pretreatment and
changes involved in whole process. This gives us important information regarding surface
structure of biosorbent also give information about completion of process. So this is the key
technique for analyzing whole process which permits the control over process.
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4 Antibiotic Antibiotic Cationic 111 freundlich Ion exchange
waste productio dye
n complex
15
5 Peach and Juice and Pb(ll) 97.6 Langmuir Coagulation
apricot stone jam
industry
16
Table no.4 use of agricultural waste as biosorbent
1.14.3 Microbial biosorbent
Microorganism are can be used as biosorbent for removing pollutant from contaminated water
reservoirs as they can tolerate unfavorable and harsh condition. They include algae fungi and
bacteria. Dead microbial biomass is preferred for binding with metal ions. Over living biomass
because they required no nutrients and monitoring of BOD and COD in effluents this make the
process more economical.
17
3 Fucus Cr(VI) 42.6 langmuir -NH,C=O,C-O,-S=O Ion exchange
vesiculolsu
18
Table no.6 bacterial biomass used for Biosorption of heavy metals
Easy to handle
Easy to grow
High yield of biomass
Ease of modification
Excellent binding with metal
Economical and echo friendly
Cell wall of fungi contains chitin and polysaccharide and polyphosphate and various metal
binding group which are hydroxyl, carboxyl, phosphate and amine. Fungal organisms are widely
used in fermentation, are easy to harvest even at industrial level. These are comparatively less
sensitive toward nutrient, pH, temperature and aeration.Because of easement of filament
separation by using filtration. Yeast is a single celled widely used as biosorbent because of high
biosorption capacity. It is found for Zn is 1699mg/g.
Cr(VI)
19
Table no.7 fungal biomass used for Biosorption of heavy metals
1.14.7 Plant as biosorbent
Plants are the best biosorbent. They can widely use. They are easily available. They can use in
both living and dead state. Dead parts of plants are making the process cheapest. Dead leaves,
stem, bark and roots are widely used for this process. Cell wall of plant is having cellulose which
are having network of hydroxyl and carboxyl groups which are having high affinity toward
metallic cations.
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1.16 Immobilization of biosorbent
Classically centrifugation and filtration were used but they were having several disadvantages
Increase in capacity
Mechanical strength
Chemical resistance
Easy separation
Nondestructive discovery
Number of matrix can be used for immobilization e.g. Silica, polysulfone, sodium alginate,
polyurethane etc. Trametes versicolor can be immobilized by using carboxyl methyl cellulose
(CMC) used for removal of Cu (ll), Pb(ll),Zn(ll) from aqua solution.
21
3 polyacrylamid pseudomonas Au langmuir carboxyl Chemisorptio
e n
Low cost
None damaging to biomass
Ensure intact metal binding capacity
Eco friendly
22
Table no.10 Desorption and regeneration of biosorbents
1.19 Factors effecting Biosorption
Biosorption is a very wide term and sensitive as well .As conclusions can be altered by various
factors like temperature, concentration of metal ion at the beginning and ending of the process,
dose of biosorbent and biosorbate, pH, solvent availability and contact time. As these are
controlling factors their variation can affect the efficiency of process.
24
amount of metal adsorbed per unit mass of biosorbent increase and vice versa. The biosorption
for Cd and Pb ions by Anabaena sphaerica can be increased as the dose of biosorbent is
increased from 0.025 to 0.25 g per 100mL solution.
1.20.2 Modification:
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Modification of biosorbent is done in many cases when there is a need to increase the affinity or
attraction between metal ion and biosorbent. As metallic ion is a constant species and no
alteration is done in it. All modifications are done on the active surface of biosorbent sometime
some negative functional groups are added as carboxyl, amide and amine to increase the
affinity of biosorbent toward metallic ion. This target is achieved with the help of seeding of
biosorbent with solution containing desired functional group for certain time of interval. By this
process biosorption capacity of biosorbent is greatly enhanced. So with the help of this
technique process become more fruitful which ultimately lead to success
1.20.5 Recovery:
With the help of UV /Vis spectrometry after certain time of interval quantity of metal ion is
quantified and when all metal is removed or we achieve our goals by removal of the heavy
metals contaminated water reservoir first need is to recover the biosorbent. This recovery
should be on the cost of structure, efficiency and quality of biosorbent should not be disturbed.
This step decide the cost of the process as on one time purchase how many time the biosorbent
can be used again and again. For greater efficiency biosorbent should be reused without any
decrease in quality and quantity. The recovery process is a very fragile step which determines
the continuation of the process with low lost. The most simple method is to treat the used
biosorbent with a precipitating agent so as to replace the adsorbed metal with the simple ion
through which this adsorbent should be ready to use again and metal is converted into the
insoluble precipitates which can be readily separated by the reaction vessel and it should be in
less harmful form. So by this method contamination is not only removed but also converted
into less harmful form and biosorbent is recovered [8], [9].
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1.21 Applications of Biosorption
In the way of progress man has created many hazards for life as well. As the result of many
processes many organic acid, heavy metals and various other pollutants are discharged into the
environment. They can be broken by physical, chemical and biological process which makes
them less harmful. But many non-biodegradable materials are not broken down into less
harmful materials can be readily discharged into environment and enter into food chain as they
are the by bioaccumulation. After that they become very essential to remove by the help of
biosorption many of these pollutants are readily eradicated from environment. Some of
important applications of biosorption process are given below:
27
1.21.6 Bioremediation
Pollutants’ can be removed from the environment by using biosorption as pollutant become
part of cellular structure of biomass. By using this environment can be cleanup without causing
any harm to atmosphere.
28
Ashfaq et al., (2019) conducted a series of experiments for the freely suspended and Ca
alginate immobilized C.vulgaris cells were used and biosorption was determined in aqua
solution for Fe (ll), Mn (ll) and Zn (ll). These analysis let them to conclude that this process is
entirely depend upon operational conditions like dosage of biosorbent, contact time between
metal and biosorbent, pH, temperature and initial and final concentration of metal maximum
value for biosorption Fe(ll) 43.43,Mn 40.98 and Zn(II) 37.23 mg/g was obtained by using Ca
alginate immobilized algal cell at optimum pH algal cell dosage was 0.6gm/L and contact time
was 450minute at room temperature[13].
Ali.A et al., (2019) examined that toxic dyes are posing a threat to life as they are permanent
part of waste water in search context magnetic separation is very effective In-situ one stepped
co precipitation is a synthetic approach developed for water dispersal
Fe3O4/chitosan/glutaraldehyde Nano composite(MCS-GA) as an efficient absorbent for the
removal of crystal violet(CV) from aqua solution. The physical and chemical properties of
MCSGA were studied by using FITER, SEM, TEM, XRD, BET and VSM techniques. The optimum
value for this process was estimated with maximum efficiency 99.99% was pH was 11 dye
concentrations was 60mg/L and MCS-GA dosage was 0.817gm/L respectively [14].
M.Jesica et al., (2019) study was based on pollutants created by industrial revolution mainly
include heavy metals. Commercial biomass of yeast Saccromyces cerevisiae was used for the
biosorption of Cu (ll). The effect of variable like pH, equilibrium time, biomass concentration
were the main point of focused by using Langmuir model with the best data detecting the
maximum biosorption capacity of 4573mg/g. biosorption capacity was also measured by many
absorption isotherm, with Langmuir, Freundlich, dubinin radushkevich(D-R) models[15].
B.D.John et al., (2019) examined the copper biosorption by using shells of sea urchin as
biosorbent from aqua solution and optimum conditions for this process is studied. A two-level
three factor phase central composite designed was used for this study and the maximum
biosorption capacity was found 14.625mg/g for 100mg/L metal solution. These results were
further confirmed by Elovich model. Optimum copper removal efficiency was found
89.09%.[16]
Z.L.Carolina et al.,(2019) study was based upon threats created by water pollutants on the
human health. As water remediation face number of challenges for effective combat against
29
pollution. Especially for developing countries having low income population so low cost
absorbent are preferred. Crustacean shells are commonly used in sea food industry they can
also serve as good biosorbent for the removal of heavy metals, heavy metals ions and
negatively charged species. This is an echo friendly method along with low cost with good
result. [17]
P.Debabrata et al.,(2019) were carried out their study by using micro algae Scenedemus sp. as
biomass as good biosorbent for the removal of toxic hexavalent Chromium or Cr(VI) from
contaminated water reservoirs. Different parameters are study like initial pH, contact time,
initial Cr (VI), and temperature were examined. It was found to be effective with maximum of
92.89Cr loading onto biomass. The FTIR analysis short biomass is having easily hydrolysable
functional groups like aldehyde, amide, carboxylic, phosphate and headiest biosorption proceed
by anionic adsorption method follow pseudo- first order kinetic model its physibilty was
confirmed by Langmuir, Freundlich isotherm. It was spontaneous and spontaneity was
increased with the increased in temperature. [18]
S.Rangabhasiyam et al., (2019) investigation was based on the use of brown algae as
biosorbent. They used brown algae turbineria conoides (TC) and Polly sulfone immobilized
turbineria conoides (PITC) used for the biosorption of rare earth metal Thulium(Tm (lll)) from
aqua solution. Higher biosorption capacity was estimated 200.5 and 157.9mg prospectively with
optimum pH 5 and contact time 200 and maximum biosorption capacity was recorded for the
initial concentration of Tm(lll) concentration 500mg/L. Recovery was done with maximum
desorption efficiency by using 0.01M HCl and HCl with 10 desorption cycles[19].
G.baeta et al.,(2019) examined emission of platinum group metals from different resources
lead to boost in concentration of platinum and palladium in sample of airborne particulate
metal savage sludge, soil and surface water for this reference Aspergillus sp. and saccharomyces
sp. Are best for the removal of Pt (VI) and Pd (ll) from aqua solution. Maximum efficiency for the
retention of platinum (IV) on yeast and fungus recorded at pH (ll) and for Pd (ll) was 2.3 to 4.5.
Equilibrium waste attainted within 45 minutes. Maximum adsorption capacity of fungus was
found 5.49mg/g for Pt (IV) and 4.28mg/g for Pd (ll)[20].
Noormuhammadi H.R et al.,(2019) examined the simultaneously biosorption od cadmium(II)
and Nickel by using living phanerochaete chrysoporium with low cost and echo friendly
biosorbent with optimization the best conditions with metal concentration Cd(II) and Ni(ll) ions
25 and 16mg/L were accumulated in P.crysosporium with efficiency of 92.6% and 89.4%
respectively at pH(6) at temperature 36˚C around 9 hours with Langmuir isotherm model
biosorption capacity was 71.4 mg/g for Cd(ll) and 46.5 mg/g for Cd(ll) respectively.[21]
30
Chu.W.L et al., (2019) industrial effluents containing heavy metals and dyes are main concern of
interest as pollutant because they are having adverse effect on human health. So they must
remove from contaminated reservoir. Heavy metal along with dyes is persistent and poisonous
as well. Physiochemio methods are not very effective in this regard by using biosorption along
with dead and living biomass they can easily remove. Biosorption capacity for microalgae is due
to high surface to volume to ratio and maximum metal binding capacity after the process
biosorbent can be recovered [22].
Escudero L.B. et al., (2018) industrial activities are mainly responsible for environment
pollution. Since their waste is toxic as well as persistent so their disposal in aqueous reservoirs
poses serious threats for aquatic and marine life and for humans as well. In this regards many
remediation techniques are used for solution biosorption play good role in clean up all this mess
with low cost technology. Maximum removal could be range from 70 to 100% was found with a
verity of biosorbent and process conditions [23].
Paul.E. et all.,(2019) industrial waste water as discharge in water reservoirs pose serious threat
to human health mainly due to presence of hazardous no biodegradable heavy metals. This
research is mainly focused on activated carbon from chicken feathers (ACCF) in the removal of
Ni (ll). FTIR was performed to check the functional groups present on the surface of ACCA.
Optimization of the factors was done by using hit and trial methods. Experimental data for Ni(ll)
sorption word treated using pseudo first order and second order kinetic models. Adsorption
behavior show it follow pseudo second order [24].
Morira V.R et all.,(2019) this study mainly focused on biosorption of Cu(ll) by using microalgae
grab the attention. As process of Cu adsorption by microalgae are serce. The adsorbent had
particle diameter ranging from 14.13 to 123.6micrones.The Langmuir isotherm model
optimization was achieved to maximum for Cu removal to 83.1% when algae concentration was
1.28gm/L at pH6.83.[25]
Albert et al.,(2019) trace metal contamination is a serious problem now a days. Fungi can best
surface in this regard.As they are capable of growing in harsh condition. This study purposed
the tolerate ability of biosorbent by Cd, Cu and Pb metals. Of 28 fungal isolates collected from
different soil sample. Each biosorbent is exposed to 50mg/L metal solution for 3 days in liquid
medium. Among 28 fungi tested absedia cylindrospora more than 45% of Cd and Pb.
Chaetomium atrobrunneum biosorbed 45% of Cd, Cu, Pb and coprinellus micaceus biosorbed
Pb100% [26].
Wang.N et al., (2019) examined lead pollution by industrial activities lead to many disorders as
mainly found in contaminated water reservoirs. For this efficient biosorbent development is the
main area interest.In this regard gram-negative bacteria Pseudomonas putida, gram-positive
bacteria Microbacteria sp. And mycelia fungus Talaromyces amestolkie serve as biosorbent
even at room temperature and maximum quantity of lead can be removed. In this regard SEM,
31
EDS,
32
FTIR, CNMR, XRD, XPS are performed to investigate the morphology of biosorbent from surface
aspect.[27]
Li.M et al.,(2019) experiments was to investigate the effect of Cr(lll) try well and chromium
biosorption by using cyano bacteria Synechocystis sp. And the effects of extra cellularpollymeric
substances EPS during process. Characteristics of Synechocystis were investigated by using FTIR
along with CNMR. Small substances like tryptophan, amino acid substances and fulvicacid acid
like substances play role in binding of Cr (lll) for biosorption. Efficacy was found about 89% at
pH
(6) with contact time 300miinutes.[28]
Oyewole.O.A et al.,(2019) examined the harmful effects created by the heavy metal pollution
as they study the biosorption of copper,chromium,cadmiu7m and nickel from polluted soil by
using fungus and bacterial culture which is isolated form soil. Bacteria were pseudomonas,
bacillus, micrococcus, eschearichi, streptococcus, Enterobacter and phylococcus while fungi
were Aspergillus niger , Pencilium, and notatum and aspergillus flavus. 5ml each day old culture
of screened bacteria and fungi was inoculated into 45ml nutrient broth and potato dextrose
broth fungi having 5, 10, 15 and 20 ppm respectively of copper, chromium, cadmium and nickel.
Temperature was 37˚C for bacteria and 28˚C for fungi in 35 days of inoculation for bacterial
isolate highest biosorption of Cr89.6% and Cu90.8% by P.aeruginosa were observed at 20ppm
on day1 and P.notatum show highest biosorption at 10ppm with 77.6% [29].
Ojima.y et al., (2019) examined biosorption process for removing heavy metals along with rare
earth metals from aqua solution. They used phosphorylated dry baker yeast as a biosorbent.
The Zeta potential of phosphorylated cells was 45mV adsorption capacity was found 1.0 m
mol/g. biosorption capacity was found to be maximum for dead biomass cells. Phosphorylated
cells possess greater negative potential so they attract metal ions rapidly and process become
feasible and economical [30].
Peng.H et al., (2019) examined the effect of using bacteria as biosorbent the process of
biosorption in which heavy material bind through the process of chilatation. Biosorption
thermodynamics and pH influence test of ochrobactrum MT180101 on ionic and chelate Copper
were investigated. The biosorption on copper by chelation required to cease the Complexation
group first through metabolic and secretory process. Biosorption of ochrobactrum MT180101
on copper involved biosorption extra cellular chelate [31].
Rahman.Z et al., (2019) examined the study of heavy metal resistance by using lead resisted
bacterium Staphylococcushomines. This implies dead biomass strain show biosorption of lead
and cadmium in single and binary system as analyzed through inductively coupled plasma
optical emission spectrometry. Living biomass exhibit more biosorption then dead biomass.
Xray defection. Energy dispersive x-ray and scanning electron microscope are used to analyze
the surface of biosorbent [32].
33
Crini.G et al., (2019) synthaticdyes are growing industry in world because of its synthetic
applications. More than 100 thousands dyes are commercially available. On the other hand they
are contaminants and very toxic as they caused cancer so they are carcinogenic.
Decontamination is very hot issue now a days so for its removal physical, chemical and
biological process area available. Cross-linked chitosan based hydrogels are most popular
biosorbent for the removal of organic dyes [33].
Jaafar.J et al., (2019) studies implies the usage of water algae for the biosorption process Cd,
Co, Fe and As from aqua solution so this method includes chlorella colonies algae for
biosorption and contact time 30h to 100h.The biosorption capacity of chlorella increased as
cadmium concentration increased from 5 to 12mg/L. at low concentration it shows
effectiveness for Cd, Co, Fe and As bioaccumulation. Maximum efficiency ranges from 95 to 98%
[34].
Lacerda.E.C.M et al., (2019) focused on the effect of metal ions concentration, biomass dose
and contact time own Cu (ll) by using Pencilium ochrochlorn. This was isolated at Sossegomine a
copper contaminated site at Brazil. Bio capacity was 7.53mg/g with maximum removal up to
75%.langmuir and Freundlich isotherm adequately described this data. This is best fungus used
for the removal of Cu (ll) ions along with recovery and regeneration process without meal
function [35].
Fernandez.M.L et al., (2019) describes the molecular characterization of the interacting
mechanism between bentonite yeast isolate, hodortorula mucilaginosa B(ll) R8. Used for the
removal of curium(lll) used as representative of trivalent actinides and europium(lll), phosphate
group were involved in the biosorption of actinides, Eu(lll),phosphate accumulate at the cell
membrane of the yeast while Cm(lll) more mobile to reach biosphere.[36]
Barquilha.C.E.R et al., (2019) studied the biosorption process by using brown algae and its
alginates as biosorbent. Sargassum sp. and its alginates are widely used for the removal of
copper and nickel from aqua solution. The process is performed in the presence of sodium
carbonate and calcium algibates beads were produced by suing dripping methods. Langmuir
model explain the data of experimental results. FTIR shows the presence of Carboxylate
sulfonic, ether, alcohol and amid group [37].
Teng.Z et al.,(2019) this examined the immobilization process for lead by phosphate by
solubilize bacteria(PSBs) is having high efficiency of immobilization specially in the formation of
insoluble lead phosphate compounds, growth feature of Leclerciea adecaboxylata a lead
resistant bacteria growth is examined in the presence of lead nightrate. Bacteria are giving
extracellular polymeric substances which capture Pb (ll) ions through lectostatic force of
attraction and iconic exchange results conclude that secretion of EPS by bacteria is one
procedure to resist heavy metal stress but also decrease bio availability of lead [38].
34
Lee.H et al., (2019) found that 3 nickel binding peptides were screened from a phage library
displayed in combination with surface engineered Saccharomyces cerevisae EBY100.
Biosorption process was enhanced by increasing number of nickel binding peptides. Orthogonal
test for yeast immobilization was designed a maximum sorption capabilities was found about
68.6 at 25˚C with
2.0 calcium chloride and 3% sodium alginate[39].
Ding et al., (2019) examined alginate immobilized aspergillus niger microsphere(AAM)
biosorbent was designed especially for the removal of thallium Th(IV). A superior biosorption
occur at pH (6) and 40˚C. This method is one which combines the superior Th (IV). Biosorption
capability, inexpensive echo friendly microbes. In addition this biomaterial has good recycle
ability through immobilization and inactivation process [40].
Morosanu.L et al., (2019) examines the biosorption process by using micro pollutants and they
used rapeseed waste as biosorbent. The purpose of their study is to remove lead ions and
reactive blue 19(Rb19) dye by using integrated approach desorption was observes for metal
ions and an ionic dye at pH2.5 and 10.5 respectively. The quadratic model generated by the
response surface methodology (RSM) adequately describes the biosorption process [41].
Roozegar.M et al.,(2019) emphasize on the removal of increasing amount of Copper(ll) from
the aqua solution by using algacystoseira Indica in this process effect of contact time, pH,initial
concentration of metal ions and different pretreatments were studied under different
condition.absoption isotherm was fitted with Langmuir model having maximum absorption
capacity of 72.1mg/g at pH(4) and 25˚C for 0.6g/L biomass.sulphonate carboxyl and amin
functional group were involved investigated by using SEMTEM x-ray, xrd and FTIR.[42]
Mora.B.E.C et al., (2019) sorption studied carried out by using ground water sample using that
column with chitosan for arsenic removal. This process was optimized by using packed column
with chitosan packing and factorial design. Elution profile was adjusted by using mathematical
methods. 68.5% As (V) removal at optimum condition. Salinity, phosphate and nitrate
concentration reduction were 60, 50 and 70% [43].
Tao.Y et al., (2019) process implies the process of sonication (20khz-kHz) was conducted to
investigate the biosorption of phenolic from blueberry pomace extraction by brewery waste
biomass.it was noticed that biosorbent capacity was enhanced by using ultrasonic field. After
sonication at 394.2W/L and 40˚C for 120m and the absorption capacity was increased 62.7% as
compared to reciprocating shaking.[44]
Giese.E.C et al.,(2019) examined the ascomycetous fungus botry of sphaeria rhodian secrete
glycan and beta glycan in large amount of mycelia biomass which is used for the adsorption for
rare earth arrangements. High adsorption capacity for both La (lll) and Sm (lll) FTIR and point of
0 charge (PZC) was quite familiar to inactive fungal cell. Rare earth element binding was
increased at pH greater than 5.lenghtnight biosorption by B.rodhina follow Langmuir model
35
[45].
36
Pi.S et al., (2019) studies were mainly focused on the pollution of sulphonamide antibiotics in
aqua solution grab the attention as the used serious threat for life. In this study interaction
mechanism of EPS from klebsiellasb sp And adsorption capacity. Biosorption capacity of EPS was
found about 70%, 55%,51% and 46.74% for SMX,SM1,SM2 and SDZ prospectively. As model
parameters show chemisorption irresponsible for adsorption and EPS has a good biosorption
capacity as indicated good biosorption capacity for sulphonamide was confirmed by SEM and
3DEEM suggest the main driving force behind this process is hydrophobic interaction of
tryptophan and tyrosine during binding process of EPS and sulphonamide [46].
Gosiaco.P.K.L et al., (2019) star fruit Averrhoa carambola found in Philippine having chelating
agents which are responsible for their biosorbent activites is used as a biosorbent against the
removal of heavy metal cadmium and lead from contaminated from water reservoirs. It was
observed that biosorption capacity for ripen fruits and unripen fruits having marked different.
The percentage of biosorption of cadmium by using unripen fruits is 45.4% while for ripe fruit is
32.3%. The lead biosorption by unripen fruits is 83 and for ripen fruit is 70.2% [48].
Azeeri.S et al., (2019) examined solid residue from prickly pear fruit seeds evaluation as a low
cost biosorbent for the removal of Cr (Vl) from contaminated reservoirs as contamination is
mainly done by tanneries. This biosorption was highly pH dependent and found maximum at
1.0 Langmuir and Freundlich fit the experiment as well. The maximum monolayer capacity was
19.61mg/g at 298k at pH1.0 thermodynamics parameter show biosorption of cadmium 6 was
spontaneous favorable endothermic activation energy was 40.6[49].
Yuan.W et al.,(2019) study is based upon remarkable biosorption capabilities of sheuanella
putrefsciens for the reduction of cadmium. As this are metal reducing bacteria. This response
surface methodology (RSM) is based upon box-behn can design which was used to optimize
these bacterium. Maximum efficiency is 86.54 under optimum condition which are contact time
was 4 days.pH value is 5 and initial concentration of cadmium was 20mg/L [50].
Chen.X et al., (2019) examined the removal of 9 pesticides residues from water and soil. As
pesticides are persistent and long lasting so they create a threat for life. Biosorbent was
prepared by peanut shell and wheat straw which act as support for the immobilization process
of a fungus called aspergillus laccase and redox mediator was involved for the improvement of
laccase catalyzed degradation called syringaldehyde(SA) with the concentration of pesticitess
and SA of 6mg/L and 1 mol/L was 54.5% and 66% within 3 days[51].
Tariq. A et al., (2019) examined the isolation of arsenic resistant bacteria which are used for the
remediation process. This strain was harvested at 37˚C broth supplemented with different
concentration of arsenate and arsinite isolated stain was belong to Pseudomonas aruginosa.
This bacterium was so efficient that its adsorption capacity was 98%. Arsenic contaminations
lead to worldwide major problem [52].
37
Suganya.P et al., (2019) examined the biosorption capacity by using plant parts as adsorbent.
The plant which was used was gliricidia sepium leaf powder. For removal of hexavalent
chromium Cr (Vl) from synthetic waste water. The optimum parameter for the maximum
removal of 99.9% with residual concentration 0.48mg/L was found at pH(ll) and contact time
was 120minutes with 0.3g of biosorbent against agitation speed of 100 rpm with initial
concentration of chromium 6 50mg/L .[53]
Lieu et al., (2019) examined the u(Vl) biosorption capacity by resistant bacterium, Bacillus,
Amyloliquefaciens which was isolated from soil. The uptake process was characterized by SEM,
TEM, FTIR and XPS. The maximum uptake capacity was 179.5mg/g at pH (6) by Langmuir model.
The thermodynamics result was ∆G˚, ∆H˚and ∆S˚ were investigated as -6.359KG/mol,
14.20kj/mol and 67.19kj/mol prospectively [54]
Adelaja O.A et al., (2019) focused on mango leaf powders remarkable by biosorption capacity
with K2S2O8 to desorb Hg2+ Congo red dye and their binary mixture. Both adsorbents
biosorption capacity was investigated by FTIR show they are having active binary sides. The
maximum removal of Hg2+ congo red dye and their binary mixture were 42.8, 54.7 and 62.5
using raw mango leaf powder at pH (7) best fitted with Freundlich and langmuir isotherm
model. [55]
Santra.B et al.,(2019) studied that textile industries are largest water consuming sector as they
used water in various process like dyeing , pretreatment, bleaching, coloring, washing, desizing
and finishing process etc. so their effluents contains unfixed dies oxillary chemicals ,salts,
bleach
, heavy metals and alkalis. Which are responsible for the water pollution at surface and ground
level. If it is not properly treated. The effluents were collected from textile dye house having
pH12 and PDS38.2 with COD3600. This was successfully involved by using ceramic membrane
driven biosorption [56]
Balkaya.N et al.,(2019) focused on the removal of the organic dye from the aqua solution by
using lignocellulolic material. Different parameters which affect these results are pH
temperature metal concentration and contact time was mainly considered. The experimental
equilibrium data best fitted with Freundlich and Langmuir isotherm. Maximum biosorption
capacity was found 263mg/g [57].
Atikpo.E et al., (2019) examined the kinetic biosorption of arsenic from contaminated soil by
using bacteria roproteus mirabillis and bacillus subtilis. This bacterium was harvested from soil
and having remarkable arcenic removal capacity. Experimental data best fitted with four kinetic
models (pseudo first order, pseudo second order, Elowhich and intraparticle Diffusion model
[58].
Tan.L et al., (2019) examined the platinum absorption capacity of Escherichia coli (E coli)
biomass for Pt(IV). The adsorption process was elucidated by using SEM, AFM, TEM, and FTIR.
38
This biosorbent is having functional groups amin, carboxyl and phosphate group. Which are
having
39
great affinity for platinum (IV) adsorption process was enlightened by from the aspect of
equilibrium, characterization and adsorption kinetics [59].
Vieira.L.C et al., (2019) reported the biosorption based technology which is suggested for the
removal of radionuclides from radioactive liquid waste containing organic compound. By using
nonliving aquatic Macrophytes lemna sp. And Pitia stratiotes used for uranium biosorption. This
study used 10ml of uranium waste and 0.2g of biomass. The equilibrium time was 1 hr. for both
species and maximum sorption capacity was found about 0.68mmol/g.[60]
Vishan.I et al., (2019) sift heavy metal pollution as environmental threat produce as a result of
anthropogenic activities and their toxic effect toward human health ultimately toward life. For
this purpose dried bacterial biomass of bacillus badius for the removal of Cd (ll). The optimum
condition were pH (7), contact time 30minutes initial biomass dosage 2g/L at temperature 40˚C
with agitation at 150rpm. The maximum biosorption capacity was 131.58mg/g was recorded.
This data best fit with Langmuir adsorption model [61].
Wang.L et al., (2019) scrutinized that microalgae present in aquatic environment have
remarkable capability to remove organic contaminants. They are very harmful for human health
as their presence can cause endocrine disruption compounds (EDCs) generation. Nonylphen
(NP) which is prior contaminant. This can be removed by intracellular adsorption, extracellular
adsorption and biodegradation of NP by 4 species of microalgae; Phagocytes globose,
Nannochloropsis oqlata, Dunaliella salina and Platymonas subcordiformis efficiency very from
the range 43 to 90% [62].
Keerthisinghe.T.P et al., (2019) chlorohexidine has broad spectrum antimicrobial having
potential threats for life. Study examined removal potential and mechanism regulating
chlorohexidine from activated sludge. Luteolibacter and runella with multi drugs resistance are
selected for this process. Antimicrobial susceptibility factor show the mount of chlorohexidine
could be lethal even in 0.4-21.3mg/L. so this study mainly implies the removal of chlorohexidine
by using 0.5g and 0.5 and 1mg/L chlorohexidine respectively with maximum removal efficiency
73.8%. [63].
40
3.1 Apparatus used:
41
Watmann filter paper no.1
Voiles
Beakers
Aluminum foil
Spatula
100ml flask
1000Ml flask
Pippete Sucker
Hot plate
Magnet
Conical flask
Oven
Wash bottle
Weighing balance
Tripod stand
Funnel
42
3.3 Preparation of stock solution
Stock solution of 1000ppm for each metal was prepared by dissolving 1.0 g of
cadmium, silver, lead and zinc metal was dissolved in appreciable amount of
distilled water in beaker. After dissolution the solution was transferred into 1000
mL volumetric flask and then it was filled with distilled water up to mark to
complete volume.
3.4 Preparation of Dilutions:
By using stock solution dilutions of 20 , 60 and 80 ppm were prepared for each
metal in 100 mL flask by using dilution formula for calculations i.e. M1V1=M2V2
3.5 Pretreatment of Sorbent:
Dead roots of Conocarpus eractus were used as biosorbent. Plant roots were
taken soaked in distilled water and then washed to get rid of soil .then for these
roots were washed with 0.1M NaOH solution then again washed with distilled
water
.them these roots were socked in 0.1 M HCl solution again washed with distilled
water, dried and crushed in plant crusher to obtain homogenous biomass.
3.6 Sorption process:
20ml of cadmium, copper, lead, silver and zinc from each dilution was taken in conical flask and
0.1g biosorbent (which is phytomass of plant roots) for biosorption. And then the flasks were
set on flask shaker at 150 rpm for 8 hours. After the interval 2 hours samples were withdrawn
and double filtered by using watmann filter paper no 1 and kept in voiles.
43
3.8 Temperature parameter:
44
Biosorption process was performed at room temperature.
q = (Ci-Ce/Ci) V/m
R% =Ci - Ce /C I *100
3.13 Freundlich Adsorption Isotherms for Silver, Cadmium, Zinc and Lead
Freundlich adsorption Isotherm was drawn for different concentration by using data obtained
as the result of experiment and regression was used for the validation of model. If the Value of
regression factor is greater than 0.9 shows model best fitted for biosorption process.
45
Optimized condition for Biosorption process:
Biosorption process was carried out by using uniform Phytomass of dead roots of Conocarpus
erectus and with maximum contact between metal and biomass was achieved by using flask
shaker with the rotation 150 rpm at room temperature and biosorption efficiency was
determined
46
after 6hours. After that no appreciable process was observed. S this can be regarded as maximum
biosorption.
Standard solution was 20.1ppm.
y = -0.805x + 19.14
2020 R² = 0.8251
16.6
15 15.2 15.1
10
0
0 1 2 3 4 5 6 7
time(hour)
47
Standard solution was 41.0 ppm of Silver
01234567
time(hour)
60 62
50
y = -4.655x + 52.09
40
R² = 0.5688
30 30 29.3 31.2
20
10
0
0 1 2 3 4 5 6 7
time(hour)
48
Biosorption Capacity of Conocarpus eractus for Silver with 20, 41 and 62ppm
solution of Silver.
62
41
31.2
29 30 29.3
20
16.6 15.2 15.1 14.7
8.59
6
02 4
1 2 3 4
Series1Series2Series3Series4
49
utilized for this work. It is estimated that quantity of biosorbent used for this process is very
50
important for this process. Because it is a direct factor which provide the binding site for the
attachment of biosorbate and it is greatly enhanced by the increase in agitation process which
lead to increase in contact ultimately enhance the biosorption capacity. As this can be inferred
by the experimental results that maximum biosorption can be achieved after the time interval
of 6 hours.
2020
15
10 y = -3.1939x + 16.129
R² = 0.7933
5 5.3106
0 0.6019 0.2772
01234567
-5 time (hours)
51
Graph is between concentrtion and time for
39.0ppm Cd solution
50
40 39
30
y = -5.7419x + 27.624
20 R² = 0.6045
10
Biosorption percentage = 93 %
Standard Solution of 61.0 ppm of Cadmium was used.
Biosorption Percentage = 91 %
Biosorption Capacity for the dead roots of Conocarpus eractus by using 20, 39 and
61 (ppm) solution of Cadmium
5
Graph is between Concentration and time
for Cadmium (20,39 and 61 ppm)
61
39
20
1 2 3 4
Series1Series2Series3Series4
Data obtained as the results inferred that the concentration of cadmium ions
decreases as the time progresses maximum adsorption was achieved at 6 hours’
time which is 98 % by using concentration 20ppm with 0.1g of biomass at room
temperature with the speed 150 rpm on flask shaker apparatus.
5
contact time was analyzed .Because contact is a direct factor which affect the efficiency of
biosorption process.
20 20.5
15
10 9.6
8.4 8.1
5
y = -1.92x + 17.41
R² = 0.6976
0
0 1 2 3 4 5 6 7
Time (hour)
Biosorption percentage=60%
5
Graph b/w Concentration and time for
Lead(41 ppm standard solution)
45
40 41
35
30
25 y = -5.17x + 31.81
20 R² = 0.6547
15
10
9.5
5 7.5 7.2
0
012 3 4 5 6 7
Time (hour)
1 2 3 4 5 y = -8.564x + 46.52 7
Time (hour) R² = 0.6257
Biosorption Capacity for the dead roots of Conocarpus eractus by using 20, 41 and
62.7 (ppm) Solution for Lead.
5
Graph b/w Contact time and Concentration for Lead(with 20.5,41&62.7s
ppm solution)
62.7
Series1Series2Series3
41
20.5
0 2 4 6
Time (hours)
Given data inferred that the falling curves show that the concentration of Lead
ions decreases as the time of contact increase. The experiment was begin with the
concentration 20.5, 41 and 62.7 ppm solutions of lead and these values gradually
decrease as the time increases. Maximum value of biosorption was achieved by
using 62.7ppm lead solution with the biosorption percentage 90% at room
temperature with the 0.1g biomass concentration and time of contact was 6
hours.
5
was
5
used and contact time was analyzed .Because contact is a direct factor which affect the efficiency
of biosorption process.
2020
15
y = -2.5x + 16.2
10R² = 0.7149
5 5.6 6
3.2
0
0 1 2 3 4 5 6 7
time (hour)
5
Graph is between concentrtion and time for
40ppm solution Zn
50
4040
30
y = -5.99x + 31.67
20R² = 0.7554
10 9
4.1
0 1.7
01234567
-10
Time (hour)
Biosorption Percentage = 96 %
time (hour)
Biosorption Percentage = 96 %
Graph is between concentrtion and time
5
Biosorption Capacity of dead roots of Conocarpus eractus by using 20, 40 and 60
(ppm) Solution for Zinc.
60
40
20
1 2 3 4
Series1Series2Series3Series4
Experimental data allow us to infer that the concentration of Zinc ions decrease as
the time progresses. Biosorption experiment was performed by using
concentration 20, 40 and 60 ppm by using 0.1g of biomass. Maximum percentage
of biosorption was obtained for the concentration 40 and 60ppm zinc solution
which is 96% with the contact time of 6 hours at room temperature.
6
Sr_No Concentration Dose Ci Ce Ci-Ce %R q Log Ce Log qe
(ppm) g
0.39
Sr No. K 1/n R2
6
Sr_no Concentration Dose Ci Ce Ci-Ce %R q Log Ce Log qe
ppm
1.07
1
0.88
0.8
0.59 0.6
y = 0.5125x + 0.9252
0.4 R² = 0.9966
0.2
0
-0.8 -0.6 -0.4 -0.2 0 0.2 0.4
log Ce
Sr_No K 1/n R2
1 0.9252 0.5125 0.9966
6
Sr_No Concentration Dose Ci Ce Ci-Ce %R q Log Ce Log qe
ppm
0.6 0.52
0.4
y = -1.0079x + 1.1997
0.2
R² = 0.2622
0
0 0.1 0.2 0.3 0.4 0.5 0.6
log Ce
Sr_No K 1/n R2
1 1.1997 -1.0079 0.2622
6
Freundlich isotherm for Silver
Sr_No K 1/n R2
1 0.711 0.025 0.003
6
Sr_No Concentration Dose Ci Ce Ci-Ce %R qe Ce/qe
ppm
2.5
2
1.5
1 1.06
Sr_No K Xm R2
1 -8.4774 0.71 0.9652
6
Sr_No Concentration Dose Ci Ce Ci-Ce %R qe Ce/qe
ppm
00.511.522.5
Ce
Sr_no K Xm R2
1 0.0371 16.6 0.9978
6
3 60 0.1 60 2.6264 57.37 96 11.47 0.22
40 38.26
30
20
16.73
10
0
00.511.522.533.5
Ce
Sr_No K Xm R2
1 67.339 -0.08 0.1989
ppm
6
Graph is between Ce and Ce/qe
6
5.5
5
4.49
4
2 y = 0.1166x + 1.7092
1.32
R² = 0.321
1
0
0 5 10 15 20 25 30 35
Ce
Sr_no k Xm R2
1 0.1166 0.5 0.321
6
3 zinc 1.1997 -1.0079 0.2627 67.339 -0.08 0.1989
As the data shows that the biosorption of Lead and Cadmium best fitted with
Langmuir and Freundlich adsorption isotherm model having value of regression
factor 0.9234 and 0.9562 for Lead and 0.9252 and 0.9978 for Cadmium
respectively. But the biosorption process for Zinc and Silver are worsely fit into
these adsorption isotherm theorem as the value of regression factor for Zinc in
Freundlich isotherm model was 0.2627 and for Langmuir it is 0.1989 similarly for
Silver values are 0.003 and 0.321 respectively which are less than 0.9.For the good
fitting of isotherm model value of regression factor is the index, which should be
greater than 0.9.