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Zn, Ni, Cu, V, Co, Average toxicity


W, Cr
As, Ag, Sb, Cd, Hg, High toxicity
Pb, U
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 pajor lead pollution is through automobiles and
battery manufacturers.
 For zinc and chromium the major application is in
fertilizer and leather tanning respectively.
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 ëeverse Osmosis
 Electrodialysis:
 Ultrafiltration:
 Ion-Exchange:
 Chemical precipitation:
 Phytoremediation
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Advantage of BIOSOëPTION over other
methods:
 Low cost;
 High efficiency;
 pinimisation of chemical and or biological
sludge;
 No additional nutrient requirement;
 ëegeneration of biosorbent; and
 Possibility of metal recovery.
Biosorption vs. Bioaccumulation
picroorganisms uptake metal either actively (bioaccumulation)
and/or passively (biosorption).
m ë  m  
 It is a metabolically passive  It is an active metabolic
process i.e. it does not process driven by energy
require energy. from respiration.
 It is more active in dead  It is active in living cells.
cells.
 It is faster and produces  It is a slower process.
higher concentration of  Toxicity affects metal uptake
metals. by living cells, but may have
 petal affinity is high under a high uptake.
favorable conditions.  Usually affected by low
 Temperature tolerance is temperature.
modest  It is only partially reversible.
 It is a reversible process
 The biosorption process involves a 
 
 
 ; biological material) and a


  normally watercontaining a
dissolved species to be sorbed ( , metal ions).
 £ue to higher affinity of the sorbent for the sorbate
species, the latter is attracted and bound there by
different mechanisms.
 The process continues till equilibrium is established
between the amount of solid-bound sorbate species
and its portion remaining in the solution.
 The degree of sorbent affinity for the sorbate
determines its distribution between the solid and
liquid phases.
m
   

 Strong biosorbent behaviour of certain micro-
organisms towards metallic ions is a function of the
chemical make-up of the microbial cells. This type of
biosorbent consists of dead and metabolically
inactive cells.

 Some microbes may collect a broad range of metals


while some are specific to certain metals.
m m

 m
 the walls of bacteria are efficient metal
chelators.
 petal binding may be at least a two-stage process ---
first involving interaction between metal ions and
reactive groups followed by inorganic deposition of
increased amounts of metal.
 The carboxyl groups of glutamic acid of
peptidoglycan is the major group for metal
deposition.
 Eg: M 
a aa  
aare used for
removal of Cr, Pb and Cd from industrial wastewater.
á 
    a      



 Algae have low nutritional requirements as they are
autotrophic and produce huge biomass
 And ,compared to bacteria and fungi produce less toxic
materials.
 Binding depends on 

   
 

 

 
 petabolism-independent accumulation of metals.
 many potential binding sites occur in algae cell walls, which
include polysaccharides, cellulose, uronic acid and proteins.

 Eg: uptake of Pb by u
   Cr (VI) by green algae
   Cu by broen seaweed M   
Ê  

 Fungal materials have high percentage of cell wall
material that shows high metal binding capacity.
 petabolism-independent binding of metal ions is
rapid and in large amounts.
 A variety of ligands may be involved including,
phosphate, hydroxyl and sulphydryl groups. carboxyl,
amino

 Some sp like á    and


u    show two phase metal uptake.
 á is found to remove Pb, Cu and Cd.
 M aa
  aa for removal of Pb, Fe,Cu, Cr.
etc.
á   

 variety of by-products are incorporated, e.g., wool,
olive cake, sawdust, pine needles, almond, and coal.
 Either protein-based animal fibres, or cellulose-based
plants fibres bear many amino, carboxylic or hydroxyl
functional groups which are used for metal uptake.
 These are inexhaustible , cheap and non-hazardous
which can be easily disposed by incineration.
 
 
 The mechanism for biosorption may be complex :

º Ion exchange
º Chelation
º Adsorption by physical forces
º Entrapment in inter and intrafibrilliar capillaries and
spaces of the structural polysaccharide network as a
result of the concentration gradient.
º £iffusion through cell walls and membranes.
 
 
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    : When transport of metals
occur across the cell membrane, it leads to
intracellular accumulation, this is dependent on cell͛s
metabolism.
 Takes place only with viable cells.
 It is often associated with an active defence
system of the microorganism, which reacts in the
presence of toxic metal.
" 
    : In this metal uptake is by
physico-chemical interaction between the metal and
the functional groups present on the microbial cell
surface.
 This is based on physical adsorption, ion exchange
and chemical sorption, which is not dependent on
the cells' metabolism.
Cell walls of microbial biomass, mainly composed of
polysaccharides, proteins and lipids have abundant
metal binding groups such as carboxyl, sulphate,
phosphate and amino groups.
This type can be relatively rapid and reversible.
 
  
      
 



   


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 Extra cellular accumulation/ precipitation


 Cell surface sorption/ precipitation and
 Intracellular accumulation.

If toxic metals are present then the method may be


dependent on cells metabolism as the cells produce
certain compounds that favor the precipitation.
  
 

 Heavy metal transport across microbial cell


membranes is mediated by the same mechanism
used to convey metabolically important ions such as
potassium, magnesium and sodium.

 This method requires cell metabolism.


 


 physical adsorption takes place with the help of van
der Waals' forces.
 biomasses of algae, fungi and yeasts ,through
electrostatic interactions between the metal ions in
solutions and cell walls of microbial cells can uptake
the metals.
#  
Cell wall of microorganisms contain polysaccharides,
the bivalent metal ions exchange with the counter
ions of the polysaccharides.
For example, the alginates of marine algae occur as salts of K+, Na+, Ca2+, and
pg2+. These ions can exchange with counter ions such as CO2+, Cu2+, Cd2+
and Zn2+ resulting in the biosorptive uptake of heavy metals
  

 The metal removal from solution may also take place
by complex formation on the cell surface after the
interaction between the metal and the active groups.
 picro-organisms may also produce organic acids
(e.g., citric, oxalic, gluonic, fumaric, lactic and malic
acids), which chelate toxic metals resulting in the
formation of metallo-organic molecules.
 These organic acids help in the solubilisation of metal
compounds and their leaching from their surfaces.
 petals may also be biosorbed or complexed by
carboxyl groups found in microbial polysaccharides
and other polymers.




 It may be either dependent on the cellular
metabolism or independent of it.
 In metabolism dependent precipitation, the biomass
react in the presence of a toxic metal producing
compounds, which favour the precipitation process.
 In the case of precipitation not dependent on the
cellular metabolism, it may be a consequence of the
chemical interaction between the metal and the cell
surface.

The various biosorption mechanisms can take place


simultaneously.
 ë  
  
 
 

 petal removal by adsorbents from water and


wastewater is strongly influenced by physico-
chemical parameters such as ionic strength, pH
and the concentration of competing organic and
inorganic compounds.

 Genetically engineered a  which expresses


Hg2+ transport system and metallothionin (a
metal binding protein) was able to selectively
accumulate 8 mole Hg2+$ cell dry weight.
    
 



 
   
 


 
   

 

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 It is the regeneration of the biosorbant and
recovering the accumulated metals.

 This metal recovery process may be destructive


or non-destructive.

 petabolism-independent biosorption is often


reversible and leads to non-destructive
desorption whereas metabolism-dependent
intracellular accumulation is often irreversible,
necessitating destructive recovery
 ëegeneration of the biosorbent is done by washing
the metal- laden biosorbent with an appropriate
solution, the type and strength of this solution would
depend on the extent of binding of the deposited
metal.

 £ilute solutions of mineral acids like hydrochloric


acid, sulphuric acid, acetic acid and nitric acid can be
used for metal desorption from the biomass.
 The desorption process should:
ͻ yield the metals in a concentrated form;
ͻ ëestore the biosorbent to close to the
original condition for effective reuse
with undiminished metal uptake and
ͻ no physical changes or damage to the
biosorbent.
m   
 Early saturation, i.e. once metal interacting sites
are occupied , uptake ceases and desorption is
required.

 The potential for biological process improvement


through genetic engg. is limited as cells are not
metabolizing.

 There is no potential for biologically altering the


metal valency state.
  
   
 %"""" At low pH the positively charged metal ions
are in competition with the protons in the soln. to
bind to the negatively charged surface of the active
site of bimass.
 So, at low pH metal uptake is less as cell wall remains
associated with H3O + ions, and the metals will face a
repulsive force.
 As the pH increases to 3-4 there͛s a subsequent
increase of negative charge , so uptake increases.
 After pH 6 there is a drastic increase in metal uptake
due to formation of metal hydroxides with their
respective metal ions.
 
 As the biomass increases the number of
binding sites for metals also increases.

 After some point sorption capacity reaches a


steady state or uptake decreases with biomass
conc. the active sites get blocked and uptake
decreases.
 

 The rate of sorption is higher at the beginning
due to more biomass which provides
increased contact between metal and
biomass.
 As the active sites in the biomass are
exhausted uptake is controlled by the rate at
which adsorbate is transferred from exterior
to interior of adsorbant.
 paximum removal time is within the first 45
min.. Equilibrium time is generally set as 4 hrs.


    

 Initial metal concentration provides an important
driving force to overcome all mass transfer resistance
of metal between aqueous and solid phase.
 At higher conc. There is an aggregation of adsorbent
particles, such aggregation leads to a decrease in the
total surface area of adsorbent and increase in
diffusion path length.
 But after a certain conc. the uptake decreases due to
the blockage of active sites.
 The initial metal conc. Should be in the range of
200-600 ppm.
#    
 Temperature effects a no. of factors for heavy metal
biosorption like :
i. Stability of initial metal ions in soln.
ii. Stability of micro organism-metal complex depending
on the site of biosorption.
iii. Effect on microorganism cell wall.
iv. The ionization of chemical moieties in the cell wall.
With increase in temp liquid viscosity decreases ,increasing
the adsorbate diffusion across the external boundary
layer.
It effects the equilibrium capacity of adsorbate depending
on whether process in exothermic or endothermic.


  
 This is a graphical representation showing a relation
between the amount adsorbed by a unit weight of
adsorbent and the amount of adsorbate remaining in
the test medium at equilibrium.
 The Langmuir and Freundlisch are the most common
models used for adsorption of metal.
 Langmuir eqn is based on some assumptions:
 All sites are equivalent
 Adsorption results in monomolecular layer of coverage.
 A molecule is adsorbed on a site independent of other
adsorbed molecules.
 Coverage is independent of binding energy and
 Constant temprature.
 
 .
The rate of attachment to the surface should be
proportional to the driving force times the area.
£riving force is the conc. In the fluid and
Area is amount of bare surface.
Affinity between biomass and diff metals is given by:

&    $'( 

Where,  is milligrams of metal accumulated per gram of the


biosorbent material;
  is the equilibrium metal concentration in solution in
mg/L;
  is the maximum specific uptake per unit mass of
adsorbent in mg/g and  is the Langmuir constant for ratio of
adsorption and desorption rates.
Ê 
  

Linear form :
&)Ê  '$

Where F and n are constant.
is conc. Of metal ion adsorbed.
  is equilibrium conc. Of metal ions .
These models can be applied at a constant pH.
These models are used in literature for modeling of
biosorption equilibrium in the presence of one
metal.