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Review Paper:
Biosorption of Heavy Metals
N. Ahalya, T.V. Ramachandra*l and RD. Kanamadi2
1. Centre for Ecological Sciences, Indian Institute of Science, Bangalore 560 012, INDIA.
2. Department of Zoology, Karnataka University, Dharwad, INDIA.
(sorbent or biosorbent; biological material) and a liquid The results showed that the biomass had a net preference
phase (solvent, normally water) containing a dissolved for copper followed b,ycadmium and zinc.
species to be sorbed (sorbate, metal ions). Due to higher
affinity of the sorbent for the sorbate species, the latter is Another inexpensive source of biomass where it is
attracted and bound there by different mechanisms. The available in copious quantities is in oceans as seaWeeds,
process continues till equilibrium is established between the representing many different types of marine macro-algae.
amount of solid-bound sorbate species and its portion However most of the contributions studying the uptake of
remaining in the solution. The degree of sorbent affinity for toxic metals by live marine and to a lesser extent freshwater
the sorbate determines its distribution between the solid and algae focused on the toxicological aspects, metal
liquid phases. . accumulation, and pollution indicators by live, metabolically
active biomass. Focus on the technological aspects of metal
Biosorbent material: Strong biosorbent behaviour of removal by algal biomass has been rare.
certain micro-organisms towards metallic ions is a function
of the chemical make"up of the microbial cells. This type of Although abundant natural materials of cellulosic
biosorbent consists of dead and metabolically inactive cells. nature have been suggested as biosorbents, very less work
has been actually done in that respect.
Some types of biosorbents would be broad range,
binding and collecting the majority of heavy metals with no The mechanism of biosorption is complex, mainly
specific activity, while others are specific for certain metals. ion exchange, chelation, adsorption by physical forces,
Some laboratories have used easily available biomass entrapment in inter and intrafibrilliar capillaries and spaces
whereas others have isolated specific strains of of the structural polysaccharide network as a result of the
concentration gradient and diffusion through cell walls and
microorganisms and some have also processed the existing membranes.
raw biomass to a certain degree to improve their biosorption
properties! There are several chemical groups that would attract
Recent biosorption experiments have focused and sequester the metals in biomass: acetamido groups of
attention on waste materials, which are by-products or the chitin, structural polysaccharides of fungi, amino and
waste materials from large-scale industrial operations. For phosphate groups in nucleic acids, amido, amino, sulphhydryl
e.g. the waste mycelia available from fermentation processes, and carboxyl groups in proteins, hydroxyls in polysaccharide
olive mill solid residues (Pagnanelli, et al 2002), activated and mainly carboxyls and sulphates in polysaccharides of
sludge from sewage treatment plants (Hammaini et al. 2003), marine algae that belong to the divisions Phaeophyta,
Rhodophyta and Chlorophyta. However, it does not
biosolids (Norton et al 2003), aquatic macrophytes
(Keskinkan et al. 2003), etc. necessarily mean that the presence of some functional group
guarantees biosorption, perhaps due to steric, conformational
Norton et al. 2003, used dewatered waste activated or other barriers.
sludge from a sewage treatment plant for the biosorption of
zinc from aqueous solutions. The adsorption capacity was Choice of metal for biosorption process: The appropriate
determined to be 0.564 mM/g of biosolids. The use of selection of metals for biosorption studies is dependent on
biosolids for zinc adsorption was favourable compared to the angle of interest and the impact of different metals, on
the bioadsorption rate of 0.299 mM/g by the seaweed the basis of which they would be divided into four major
Durvillea potatorum (Aderhold et al. 1996). Keskinkan et categories: (i) toxic heavy metals (ii) strategic metals (iii)
al. 2003 studied the adsorption characteristics of copper, zinc precious metals and (iv) radio nuclides. In terms of
and lead on submerged aquatic plant Myriophyllum spicatum. environmental threats, it is mainly categories (i) and (iv) that
are of interest for removal from the environment and/or from
The adsorptioncapacities were 46.69 mg/g for lead, 15.59
mg/g for zinc and 10.37 mg/g for copper. Table 1 gives a point source effluent discharges.
comparison of heavy metal uptakes of various macrophytes. Apart from toxicological criteria, the interest in
Pagnanelli, et al2002 have carried out a preliminary specific metals may also be based on how representative their
study on the 'Useof olive mill residues as heavy metal sorbent behaviour may be in terms of eventual generalization of
material The results revealed that copper was maximally results of studying their biosorbent uptake. The toxicity and
adsorbed in the range of 5.0 to 13.5 mg/g under different interesting solution chemistry of elements such as chromium,
operating conditions. arsenic and selenium make them interesting to study.
Strategic and precious metals though not environmentally
The simultaneous biosorption capacity of copper, threatening are important from their recovery point of view.
cadmium and zinc on dried activated sludge (Hammaini et
al. 2003) were 0.32 mmol/g for metal system such as Cu- Biosorption Mechanisms: The complex structure of
Cd; 0.29 mmol/g for Cu-Zn and 0.32 mmol/g for Cd-Zn. microorganisms implies that there are many ways for the
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Res. J. Chern.Environ.
metal to be taken up by the microbial cell. The biosorption across the cell membrane. ( Costa, et.al., 1990, Gadd et.al.,
mechanisms are various and are not fully understood. They 1988, Ghourdon et.al., 1990, Huang et.al., 1990., Nourbaksh
may be classified according to various criteria. et.al.,1994)
According to the dependence on the cell's Physical adsorption: In this category, physical adsorption
metabolism, biosorption mechanisms can be divided into: takes place with the help of van der Waals' forces. Kuyucak
and Volesky 1988, hypothesized that uranium, cadmium,
1. Metabolism dependent and
zinc, copper and cobalt biosorption by dead biomasses of
2. Non -metabolism dependent. algae, fungi and yeasts takes place through electrostatic
interactions between the metal ions in solutions and cell walls
According to the location where the metal removed
of microbial cells. Electrostatic interactions have been
from solution is found, biosorption can be classified as
demonstrated to be responsible for copper biosorption by
1. Extra cellular accumulation/ precipitation bacterium Zoogloea ramigera and alga Chiarella vulgaris
2. Cell surface sorption! precipitation and (Aksu et al. 1992), for chromium biosorption by fungi
3. Intracellular accumulation. Ganoderma lucidum and Aspergillus niger .
Transport of the metal across the cell membrane Ion Exchange: Cell walls of microorganisms contain
yields intracellular accumulation, which is dependent on the polysaccharides and bivalent metal ions exchange with the
cell's metabolism. This means that this kind of biosorption counter ions of the polysaccharides. For example, the
may take place only with viable cells. It is often associated alginates of marine algae occur as salts of K+,Na+,Ca2+,and
with an active defense system of the microorganism, which Mg2+.These ions can exchange with counter ions such as
reacts in the presence of toxic metal. C02+,Cu2+,Cd2+and Zn2+resulting in the biosorptive uptake
of heavy metals (Kuyucak and Volesky 1988). The
During non-metabolism dependent biosorption, biosorption of copper by fungi Ganoderma lucidium
metal uptake is by physico-chemical interaction between the (Muraleedharan and Venkobachr, 1990) and Aspergillus
metal and the functional groups present on the microbial cell niger was also uptaken by ion exchange mechanism.
surface. This is based on physical adsorption, ion exchange
and chemical sorption, which is not dependent on the cells' Complexation: The metal removal from solution may also
metabolism. Cell walls of microbial biomass, mainly take place by complex formation on the cell surface after
composed of polysaccharides, proteins and lipids have the interaction between the metal and the active groups. Aksu
abundant metal binding groups such as carboxyl, sulphate, et al. 1992 hypothesized that biosorption of copper by C.
phosphate and amino groups. This type of biosorption, i.e., vulgaris and Z. ramigera takes place through both adsorption
non-metabolism dependent is relatively rapid and can be and formation of coordination bonds between metals and
reversible (Kuyucak and Volesky, 1988). amino and carboxyl groups of cell wall polysaccharides.
Complexation was found to be the only mechanism
In the case of precipitation, the metal uptake may responsible for calcium, magnesium, cadmium, zinc, copper
take place both in the solution and on the cell surface (Ercole, and mercury accumulation by Pseudomonas syringae. Micro-
et al. 1994). Further, it may be dependent on the cell's' organisms may also produce organic acids (e.g., citric, oxalic,
metabolism if, in the presence of toxic metals, the gluonic, fumaric, lactic and malic acids), which may chelate
microorganism produces compounds that favour the toxic metals resulting in the formation of metallo-organic
precipitation process. Precipitation may not be dependent molecules. These organic acids help in the solubilisation of
on the cells' metabolism, if it occurs after a chemical metal compounds and their leaching from their surfaces.
interaction between the metal and cell surface.
Metals may be biosorbed or complexed by carboxyl groups
Transport across cell membrane: Heavy metal transport found in microbial polysaccharides and other polymers.
across microbial cell membranes may be mediated by the Precipitation: Precipitation may be either dependent on
same mechanism used to convey metabolically important ions the cellular metabolism or independent of it. In the former
such as potassium, magnesium and sodium. The metal case, the metal removal from solution is often associated
transport systems may become confused by the presence of with active defense system of the microorganisms. They react
heavy metal ions of the same charge and ionic radius in the presence of a toxic metal producing compounds, which
associated with essential ions. This kind of mechanism is
favour the precipitation process. In the case of precipitation
not associated with metabolic activity. Basically biosorption not dependent on the cellular metabolism, it may be a
by living organisms comprises of two steps. First, a consequence of the chemical interaction between the metal
metabolism independent binding where the metals are bound and the cell surface. The various biosorption mechanisms
to the cell walls and second, metabolism dependent mentioned above can take place simultaneously.
intracellular uptake, whereby metal ions are transported
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Use of Recombinant bacteria for metal removal: Metal by different microorganisms seemed to be completely
removal by adsorbents from water and wastewater is strongly inhibited by the presence of uranium, lead, mercury and
influenced by physico-chemical parameters such as ionic copper (Sakaguchi and Nakajima, 1991).
strength, pH and the concentration of competing organic and
inorganic compounds. Recombinant bacteria are being Biosorption equilibrium models - Assessment of sorption
investigated for removing specific metals from contaminated performance: Examination and preliminary testing of solid-
water. For example a genetically engineered E.coli, which liquid sorption system are based on two types of
expresses Hg2+transport system and metallothionin (a metal investigations: (a) equilibrium batch sorption tests and (b)
binding protein) was able to selectively accumulate 8 /lmole dynamic continuous -flow sorption studies.
Hg2+/g cell dry weight. The presence of chelating agents The equilibrium of the biosorption process is often
Na+,Mg2+and Ca2+did not affect bioaccumulation. described by fitting the experimental points with models
Factors affecting Biosorption : The investigation of the (Gadd, et al. 1988) usually used for the representation of
efficacy of the metal uptake by the microbial biomass is isotherm adsorption equilibrium. The two widely accepted
essential for the industrial application of biosorption, as it and linearised equilibrium adsorption isotherm models for
gives information about the equilibrium of the process which single solute system are given by the following:
is necessary for the design of the equipment. qrn"" b C eq Lan gmuir
q=
The metal uptake is usually measured by the 1+ b Ceq
parameter 'q' which indicates the milligrams of metal
where q is milligrams of metal accumulated per gram
accumulated per gram of biosorbent material and 'qH' is of the biosorbent material; C eq is the metal residual
reported as a function of metal accumulated, sorbent material
used and operating conditions. concentration in solution; qrnax
is the maximum specific uptake
corresponding to the site saturation and b is the ratio of
The following factors affect the biosorption adsorption and desorption rates. This is a theoretical model
process: for monolayer adsorption.
1. Temperature seems not to influence the biosorption Another empirical model for monolayer adsorption
performances in the range of 20-35 CC(Aksu et al. 1992) IS
q= K F C eq IIn Freundlich
2. pH seems to be the most important parameter in the
biosorptive process: it affects the solution chemistry of
where KF and n are constants.
the metals, the activity of the functional groups in the
biomass and the competition of metallic ions (Friis and These models can be applied at a constant pH. These
Myers-Keith, 1986, Galun et al. 1987) models are used in literature for modeling of biosorption
3. Biomass concentration in solution seems to influence equilibrium in the presence of one metal. These values are
plotted in a 2D line where the specific uptake q is reported
the specific uptake: for lower values of biomass
concentrations there is an increase in the specific uptake
as a function of the metal concentration Ceq . .
(Fourest and Roux, 1992; Gadd et al. 1988). Gadd et al. But the above said adsorption isotherms may exhibit
1988 suggested that an increase in biomass concentration an irregular pattern due to the complex nature of both the
leads to interference between the binding sites. Fourest sorbent material and its varied multiple active sites, as well
and Roux, 1992 invalidated this hypothesis attributing as the complex solution chemistry of some metallic
the responsibility of the specific uptake decrease to metal compounds (Volesky and Holan, 1995). Evaluation of
concentration shortage in solution. Hence this factor
equilibrium sorption performance needs to be supplemented
needs to be taken into consideration in any application
of microbial biomass as biosorbent. by process-oriented studies of its kinetics and eventually by
dynamic continuous flow tests.
4. Biosorption is mainly used to treat wastewater where
more than one type of metal ions would be present; the Bioso.rption by immobilized cells: Microbial biomass
removal of one metal ion may be influenced by the consists of small particles with low density, poor mechanical
presence of other metal ions. For example: Uranium strength and little rigidity. The immobilization of the biomass
uptake by biomass of bacteria, fungi and yeasts was not in solid structures qeates a material with the right size,
affected by the presence of manganese, cobalt, copper, mechanical strength and rigidity and porosity necessary for
cadmium, mercury and lead in solution (Sakaguchi and metal accumulation. Immobilisation can also yield beads and
Nakajima, 1991). In contrast, the presence of Fe2+and granules that can be stripped of metals, reactivated and re-
Zn2+wasfound to influence uranium uptake by Rhizopus used in a manner similar to ion exchange resins and activated
arrhizus (Tsezos and Volesky, 1982) and cobalt uptake carbon.
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Research Journal Of Chemistry And Environment. Vol. 7 (4) Dec. (2003)
Res. J. Chern.Environ.
Pencillium digitatum also showed enhancement of cadmium, metals from industrial effluents. The development of the
nickel and zinc biosorption. Removal of surface impurities, biosorption processes requires further investigation in the
rupture of cell-membrane and exposure of available binding direction of modeling, of regeneration of biosorbent material
sites for metal bioadsorption after pre-treatment may be the and of testing immobilized raw biomasses with industrial
reason for the increase in metal bioadsorption. McGahren et effluents. Due to the extensive research and significant
al. (1984), Brierly etal (1985) and Muraleedharan and economic benefits of biosorption, some new biosorbent
Venkobachar (1990) showed that alkali treatment of biomass materials are poised for commercial exploitation.
may destroy autolytic enzymes that cause putrefaction of
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M.spicatum
capacity for metal ions (Yan and Viraraghavan, 2000). Hence,
the bioadsorption efficiency of dead biomass may be greater,
(Keskinkan et al. 2003) I 46.69 I 15.59 I 10.37
equivalent to, or less than that oflive biomass depending on M.spicatum
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(SchneiderandRubio,1999) I - I 18.1 I 19.7
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E.crassipes
Biosorption is being demonstrated as a useful I - I 19.2 I 23.1
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Research Journal Of Chemistry And Environment, Vol. 7 (4) Dec. (2003)
Res. J. Chern.Environ.
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View publication stats (Received 4th September 2003, accepted 15th November 2003)