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Advancement of Chitosan-Based Adsorbents for Enhanced

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and Selective Adsorption Performance in Water/Wastewater

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ABSTRACT
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This paper gives an overview of the results obtained by various researchers in the treatment of various
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suspensions and solutions by using chitosan. Adsorption techniques are widely used to remove
certain classes of pollutants from water and wastewater. Besides conventional adsorbents
there are so many alternative non-conventional sorbents have been investigated. It is well-
known that natural materials, waste materials from industry and agriculture and biosorbents
can be obtained and employed as inexpensive sorbents. In this review, Chitosan, a partially
deacetylated polymer obtained from the alkaline deacetylation of chitin, a biopolymer

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extracted from shellfish sources has been reviewed for its application in water and

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wastewater pollution as an adsorbent. Chitosan exhibits a variety of physicochemical and

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biological properties resulting in numerous applications in fields such as cosmetics,
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biomedical engineering, pharmaceuticals, ophthalmology, biotechnology, agriculture,
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textiles, oenology, food processing and nutrition. Application of chitinous products in
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wastewater treatment has received considerable attention in recent years in the literature. This
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review highlights some of the notable examples in the use of chitosan and its grafted and cross
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linked derivatives for removal of metal ions, dyes from aqueous solutions. The review provides a
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summary of recent information obtained using batch studies and deals with the various adsorption
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mechanisms involved. The effects of parameters such as the chitosan characteristics, the process
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variables, the chemistry and the solution conditions used in batch studies on the biosorption capacity
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are presented and discussed. The review also summarizes and attempts to compare the equilibrium
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and kinetic modeling. It is attempted to identify the gaps in the use of Chitosan as an adsorbent and to
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indicate future directions useful for research.

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Key Words: Chitosan, Chitin, Adsorption, Sorbents, Batch Process, Modeling,

1.0 INTRODUCTION: planet earth. The root cause of environmental

Pollution is the most serious ecological crisis pollution has been the man¶s misbehavior with
to which we are subjected today. The main the nature under the false ego of being the
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causes include the rapid urban-industrial master of nature. This undesirable situation
technology revolution, hurriedly exploitation created by man has threatened the survival of
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of natural resources by man, population man himself and other living biota on the
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explosion etc. Today the environment has earth.

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become foul, contaminated, undesirable, and

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therefore harmful for the health of living

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organisms, including man. The fabulous 1.1 Water pollution:

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plentifulness of nature is a heritage that should The earth is the blue planet. Water is a vital
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never be spoiled. But the unlimited voracious natural resource, which is essential for variety
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exploitation of nature by man has disturbed the of purposes. It is an essential constituent of all
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delicate ecological balance existing between animal and vegetable matters. It is also an
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living and non-living components on the essential ingredient of animal and plant life. Its
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uses include drinking and other domestic uses, iv) Pesticides and Fertilizers v) Soap and

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industrial cooling, power generation, Detergents vi) Thermal Pollution etc.

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agriculture, transportation and also waste Heavy metals concentration in above sources

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disposal. At the present state of national found to be more; consequently it is essential

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development, agricultural productivity in India to study in lengths.

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is profoundly dependent on rainfall. Droughts 1.3 Pollution by Heavy Metals:

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due to less rain in various parts of our country
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during the last decade, have given a series of aquatic ecosystems because some of these
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jolts to the growth of our economy. Growing metals are potentially toxic, even at very low
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population, accelerating pace of concentrations. Additionally, heavy metals are
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industrialization and intensification of not biodegradable and tend to accumulate in
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agriculture and urbanization exert heavy living organisms, and they can cause severe
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pressure on our water resources. With the problems to both human health and wildlife
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increase in the age of the earth, clean water is (Crini, 2005). Natural processes and human
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becoming more precious because water is
being polluted by several manmade activities,
e.g. rapid population growth, alarming speed
of industrialization and deforestation,
urbanizations, increasing living standards and
wide spheres of other human activities.
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activities have polluted and reduced the
quality of water resources all over the world.
Groundwater and superficial water have been
contaminated in various ways; e.g. by mining
wastes including cyanide and toxic heavy
metals, by agricultural chemicals, by industrial

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Ground water, surface water and water from and domestic sewage that is sometimes
river, sea, lakes, ponds etc one getting polluted discharged without treatment into waterways

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very rapidly. The term water pollution refers and by natural trace elements (e.g. arsenic).

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to anything causing change in the diversity of Since it is important to eliminate or reduce the
aquatic life. The presence of too much of at
concentration of heavy metals in the aquatic
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undesirable foreign substance in water is ecosystems, various methods and technologies
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responsible for water pollution. Water are commonly applied in the treatment of
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pollution is one of the most serious problems mining and refining industry effluents before
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faced by man today. Since water is the vital they are discharged to receiving water. These
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concern for mankind and essential for methods include precipitation, ion exchange,
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erudition, animal and aquatic life. It is the and membrane processes. However, the
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universal enabling chemical which is capable application of some of these methods may be
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of dissolving or carrying in suspension of a impractical due to economic constraints or

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variety of a toxic materials from mainly heavy may be insufficient to meet strict regulatory
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flux of sewage, industrial effluents, domestic requirements. Furthermore, they may generate
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and agricultural waste. Plant nutrients, hazardous products or products which are
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pesticides, insecticides, herbicides and difficult to treat (Gavrilescu, 2004; Reddad et

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fertilizers plants and animal debris are reported
to cause heavy pollution to water sources.
Nowadays fertilizers containing phosphates
and nitrates are added to soil, some of these
are washed off through rainfall, irrigation and
drainage into water bodies¶ thereby severely
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al., 2002). The traditional coagulation and
flocculation processes use inorganic
coagulants such as aluminium hydroxides in
drinking water treatment. Metal coagulants
can be used to partially remove heavy metal
from wastewater ,but the use of metal

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disturbing aquatic system. Organic wastes coagulants is not fully effective for removing
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increase the BOD of the receiving water body. metal cations from water at pH 7 (Bell and
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Some pesticides, which are non- Saunders, 2005). The high cost of adsorbents
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biodegradable, when sprayed, remain in the such as activated carbon and some ion-
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soil for longer time and then are carried in exchange resins used for the treatment of
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water bodies during rainfall. That is why it is water and wastewater have found to be more
of special interest to study the water pollution. effective and cheaper adsorbents. Bailey et al.,
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1.2 Sources of Water Pollution: (1999) mentioned that natural materials that
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Sources of contamination of water can be are available in large quantities or industrial

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classified as follows: waste products can also be used as adsorbents.

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i) Sewage and Domestic Wastes. ii) Industrial Chitin and its deacetylated form, chitosan, are
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Effluents iii) Agricultural Discharges two biopolymers that come from crustacean
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shells and have the ability to fix a great variety 2.1 Chitin and Chitin:

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of heavy metals (Muzzarelli, 1977). The Chitin and chitosan are nitrogenous

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relatively high proportion of nitrogen sites polysaccharides that are made up of

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explains the strong affinity of metal ions for acetylglucosamine and glucosamine units. In

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these sorbents. The use of these biopolymers fact, these two polymers have exactly the same

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can be a low cost alternative for the removal of basic chemical structure: (1ĺ4)-2-acetamido-

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contaminants from industrial effluents and
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from the natural water supply and is hence deoxy-ȕ-D-glucan , respectively. The
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chosen for detailed study in this paper. difference between them is the deacetylation
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degree (DD) and their respective solubility in
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2.0 CHITOSAN AS AN ADSORBENT: dilute acidic media. Sorlier et al., (2001)
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The metal sorption capacity of chitosan varies showed that chitosan is the only derivative to
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with crystallinity, affinity for water, be soluble at a DD above 40%. Chitosan is a
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deacetylation degree and amino group content. biodegradable, nontoxic extract from shellfish
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Kinetic studies have demonstrated that the rate
of metallic ion sorption onto chitosan differs
depending on the raw material (shrimp, crab or
lobster shells), preparation method, chemical
modification, and chitosan particle shape. Wu
(2000) evaluated the sorption capacities and
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shells used in a variety of water purification
applications. Chitosan is derived from chitin
(pronounced ky-tin), nature¶s second most
abundant biopolymer and primary constituent
of shellfish shells, insect exoskeletons, and
fungi cell walls. Chitosan is so safe that it is

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rates for Cu (II) onto flakes and bead forms of used in commercial aquariums to clarify the
chitosan prepared from fishery wastes. They water in the aquarium exhibits and it is also

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found that the bead type of chitosan exhibited used to clarify public pools and spas. In

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a greater sorption rate than the flake type. On addition to its safety record, the secret of its
the other hand, Ngah Wan et al., (2004) at
success is the way in which it interacts with
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performed kinetic studies of Cu (II) sorption sediment particles. Chitosan creates a fibrous
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on chitosan beads and chitosan/PVA beads, web linking the sediment particles together in
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and reported that the pseudo-second-order rate a three-dimensional matrix. When this matrix
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constant of chitosan beads was higher than the enters a sand filter it is caught in the sand but
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rate constant of chitosan/PVA beads. The allows the water through, but other polymers
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sorption process also depends on the and coagulants form a gelatinous floc that
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physicochemical characteristics of the aqueous rapidly clogs filters. Chitosan allows

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solutions, such as pH, temperature, metallic extremely long filtration cycles at sediment
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ion concentration and the form of the main loading rates that are well above industry
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species in the solution (Guibal, 2004). For standards. Chitin occurs in nature as ordered
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example, it is observed that the uptake of As crystalline micro fibrils forming structural
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(V) is greater than As (III) onto chitosan components in the exoskeleton of arthropods
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(Boddu et al., 2007), and that it depends
greatly on the pH and redox conditions and on
the temperature (Gerente et al., 2005) .The
design of a chitosan filter for the removal of
metallic ions from contaminated effluents
requires equilibrium and kinetic data for the
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(Rinaudo, 2006), its major source being the
seafood crustacean (crab, shrimp, prawn, and
lobster shells) that is usually disposed as waste
material. Depending on its source, three
different crystalline polymorphic forms of
chitin have been identified: Į-chitin (shrimp

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system. Numerous studies have demonstrated and crab shells), ȕ-chitin (squid pen), and Ȗ-
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that chitosan possesses a great sorption chitin (stomach cuticles of cephalopoda) (Jang
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capacity and favorable kinetics for most et al., 2004) Chitin is a white, hard, inelastic,
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metals. Simplified kinetic models have been and inert solid. It is highly hydrophobic and is
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used to determine the sorption mechanisms insoluble in water and most other organic
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and potential rate-controlling steps, such as solvents. It is soluble in

external and intra-particle mass transfer as hexafluoroisopropanol, hexafluoroacetone,
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well as adsorption of copper and zinc onto and chloroalcohols in conjugation with
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chitosan. These models have incorporated the aqueous solutions of mineral acids (Ravi
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pseudo first-order, pseudo-second-order, and Kumar, 2000). When the deacetylation degree
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intra-particle diffusion equations. of chitin drops to about 50%, it becomes

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soluble in aqueous acidic media and is called

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chitosan (Rinaudo, 2006). The production of often to remove residual pigments. Chitosan is

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chitin involves chemical or enzymatic produced at an industrial level by chemical

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deproteinisztion and acid treatment to dissolve deacetylation of chitin using sodium hydroxide

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calcium carbonate. In addition, discoloration is (see Figure µ1¶)

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Figure (1): Scheme of chemical deacetylation of chitin to produce chitosan
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but chitosan can also be produced by
enzymatic deacetylation of chitin using
lysozyme, snailase, neutral protease, and chitin
deacetylase (Cai et al., 2006). Due to the free
amino groups in chitosan, this polymer
chelates five to six times¶ greatest amounts of
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of valuable metals), and analytical purposes.
However, chitosan has not found any practical
applications on an industrial scale because of
the cost of material, the variability in the
characteristics of the material, and the
availability of the resource (Guibal, 2004).

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metals than chitin (Bailey et al., 1999). 2.2 Characteristics of Chitosan:

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Muzzarrelli (1977) found that chitosan is Chitosan is a semi crystalline polymer in the

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selective with regard to the sorption of metal solid state (Rinaudo, 2006). Chitosan has been

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ions. It does not take up alkali and alkali earth shown to be biologically renewable,
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metal ions but it collects transition and post- biodegradable, biocompatible, non-antigenic,
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transition metal ions from the aqueous non-toxic and biofunctional (Malafaya et al.,
solution. These sorption properties have been 2007). The characteristics of seafresh chitosan
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used for environmental purposes (uptake of are mentioned in Table -1.

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heavy metals), separation processes (recovery

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Table-1: Characteristics of Chitosan

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Item Characteristic
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1.Appearance Yellowish
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2.particle size Mesh no.60

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3.ash content 0.83%

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4.moisture content 8.5%

5.deacetylation degree(%DAC) 86%
6.Solution(1% in 1% acetic acid)
Insoluble 0.59%
Viscosity 152cps
7.Heavy metals 0 ppm
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Total Plate count 50
Yeast and Mould 20
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E.coli Nil
Salmonelia Nil
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Source: Seafresh Chitosan (Lab), (2000).

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The main parameters for its characterization chemical and biological properties (Sorlier et
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are the deacetylation degree (DD), the al., 2001). The deacetylation degree controls
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crystallinity and the polymer molecular weight the fraction of free amino groups that will be
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(Guibal, 2004). These parameters may affect available for interactions with metals ions.
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its conformation in solution, and its physico- Infrared spectroscopy and NMR analysis are
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the most common methods to evaluate the
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deacetylation degree. Infrared spectra of
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chitosan are usually obtained with a frequency
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range of 4000±400 per cm and the degree of
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deacetylation (DD) is given by equation
(Domszy and Roberts, 1985), In contrast,
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Guibal (2004) asserted that rather than the
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deacelylation degree it is better to consider the
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total number of free amino groups accessible
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to metal uptake, since some amino groups can
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be involved in hydrogen bonds. This can be
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controlled by the residual crystallinity, which
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can be influenced by the experimental
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preparation procedure and the origin of the
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raw material. Methods used to decrease the
crystallinity involve the dissolution of chitosan
(in acid solution) followed by a coagulation
process and direct freeze-drying of the
polymer solution. The crystallinity of the
polymer can be measured by X-ray diffraction.
A simple method to determine the chitosan
molecular weigh is viscometry (Ravi Kumar,
2000). The polymer molecular weigh may be
found by applying the Mark-Houwink
equation:
[Ș] = KMĮ, where [Ș] is the intrinsic viscosity
and M is the molecular weight. Į and K are
experimental values which can be determined
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in several solvents.
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2.3 Modified Chitosan
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Chitosan can be modified by chemical or
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physical processes in order to control the
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reactivity of the polymer or enhance the
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sorption kinetics depending on the field of
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application (Guibal, 2004). Two basic types,
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namely, physical and chemical are discussed
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below:
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2.3.1 Physical Modification
Various techniques have been used to
physically modify chitosan, obtaining
conditioned polymer forms such as powders,
nano particles, and gels (beads, membranes,
sponge, honeycomb, fibers or hollow fibers).
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Several studies have demonstrated that the
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particle size plays an important role in the
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uptake of metallic ions. Ng et al. (2003) found
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that the uptake of Pb ions depends on the
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inverse of the particle sizes. Chitosan nano
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particles (between 40 and 110 nm) produced
by ionic chelation of sorbent were used to
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remove lead from aqueous solution. A
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decrease in the particle size of the chitosan
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improved the adsorption capacity for lead ions.
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In addition, a decrease in the crystallinity of
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sorbent was observed (Qi and Xu, 2004).
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Guibal (2004) mentioned that, due to the
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resistance of intra-particle mass transfer, the
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use of small particles is necessary. However,
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these can be inappropriate for a column system
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because they can lead to hydrodynamic
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limitations. To improve diffusion properties
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and hydrodynamic behaviour, chitosan gel
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beads can be used. However, the adsorption
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capacity for metallic ions usually decreases.
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Chen and Chung (2006) reported a low uptake
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for As(III) and As(V) using gel beads
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compared with other studies using chitosan.
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Spherical gel beads of different sizes and
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porosities, membranes, and fibers can be
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prepared using neutralization methods. Gel
beads are obtained by adding an acetic acid
chitosan solution drop wise to a 1M NaOH
solution with a micro syringe (Krajewska,
2005). Chitosan membranes can also be
prepared from chitosan solutions in acetic
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acid. The solution is poured into a Petri dish
and, after the solvent has evaporated, the
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membrane is neutralized with sodium
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hydroxide (Guibal, 2004). Furthermore,
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porous three-dimensional sponges can be
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prepared by freeze-drying, where chitosan
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solutions or gels are frozen followed by
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lyophilisation. The porosity and morphology
of the material produced depends on the
chitosan molecular weight and on the
composition and concentration of the starting
solution, and most importantly on the freezing
temperature and freezing rate (Krajewska,
2005).
2.3.2 Chemical Modification:
Chemical modification of chitosan has two
main aims: (i) to improve the metal adsorption
properties, and (ii) to change the solubility
properties of chitosan in water or acidic
medium. These include substitution reactions,
chain elongation (cross-linking, graft
copolymerization, and polymer networks), and
depolymerisation (chemical, physical, and
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enzymatic) (Harish Prashanth and
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Tharanathan, 2007).The insertion of functional
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groups in the chitosan may involve the ±NH2
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group at the C-2 position (specific reactions)
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or ±OH groups at the C-3 and C-6 positions
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(non specific reactions) (Rinaudo, 2006). In
fact, the preparation of water-soluble chitosan
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derivatives was carried out by simple N, O±
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acetylation using AcCl and Ac2O in MeSO3H,
where the degree of substitution of the NHAc
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group was 0.15±0.29 and that of the OAc
group was around 1.0 (Hitoshi et al.,
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2002).The modification of chitosan to produce derivates have also been obtained by grafting

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Schiff bases may improve its capacity to new functional groups: (a) to increase the

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interact with metallic ions. These Schiff bases density of sorption sites, (b) to change the pH

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can be obtained via a reaction with aldehydes range for metal sorption, (c) to change the

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and ketones (Muzzarelli et al., 1985), with sorption sites with the purpose of increasing

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aromatic aldehydes in acetic acid (Tirkistani, sorption selectivity for the target metal

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1998), and with salicylaldehyde and five
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derivatives: 5±brome, 5±chlorine, 5±nitro, 5± (methyl acrylate) and poly [1-
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methyl, and 5±methoxy (Dos Santos et al., (methoxycarbonyl) ethylene] onto chitosan,
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2005). Other chitosan derivatives produced by poly-ȕ(1ĸ 4)-2-amino-2-deoxy-d-glucose, has
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substitution reactions are O± and N± also been investigated. The grafting reaction
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carboximethyl chitosan, an amphoteric was carried out in aqueous solution using
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polymer; chitosan 6±O±sulphate, an ferrous ammonium sulphate (FAS) in
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anticoagulant; N±methylene phosphonic combination with H2O2 as redox initiator. The
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chitosan, an anionic derivative; and trimethyl
chitosan ammonium, a cationic derivative
(Rinaudo, 2006). An important chitosan
derivative for the effective uptake of As (III)
and As (V) from aqueous solution is
molybdate-impregnated chitosan beads
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grafted chitosan was found to be insoluble in
solvents, which normally dissolve chitosan.
The results showed that the graft copolymer
was thermally more stable than pure chitosan
(Yazdani-Pedram et al., 1995). Additionally,
the grafting of phosphate or phosphonic

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(Dambies et al., 2002). This derivative can be groups onto chitosan promoted the uptake of
prepared by the molybdate adsorption and some alkaline and alkaline-earth metals (e.g.

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coagulation methods. The possibility of calcium and sodium) (Guibal, 2004). The

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extending the uptake of metallic ions from degradation products of chitosan, such as low
acidic medium has motivated the production at
molecular weight chitosan (LMWC),
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of cross linked chitosan. The cross-linking chitooligosaccharides (COS), and monomers,
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method improves the acidic stability of were found useful for biomedical applications.
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chitosan. However, this process may cause a Chemical, physical or enzymatic

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decrease in the adsorption capacity of the depolymerisation has been used to produce
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sorbent, especially in the case of chemical these products (Harish Prashanth and
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reactions involving amino groups (Guibal, Tharanathan, 2007).

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2004). These derivatives can be obtained by 2.4 Applications of Chitosan:

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reaction of chitosan with different Chitosan has a wide range of applications

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di/polyfunctional reagents such as which depend on its physical, chemical, and

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tripolyphosphate (Lee et al., 2001), biological properties. The principal areas are
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formaldehyde (Desai, 2005), gluteraldehyde agriculture, drinking water and wastewater

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(Jeon and Höll, 2003), ethylene glycol treatment, food and beverages, cosmetics and
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diglycidyl ether (Li and Bai, 2006),
hexamethylene diisocyanate (Arrascue et al.,
2003) or cross-linked N-carboximethyl
chitosan (Muzzarelli et al., 1989).Chitosan
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toiletries, biomedics and pharmaceutics, fibers
and textiles, and paper technology (Rinaudo,
2006; Ravi Kumar, 2000). A summary of the
main applications are presented in Table-2.

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Table- 2: Applications of Chitosan

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Area Application Reference

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Agricultural Coating of fertilizers, pesticides, herbicides, Krajewska (2005)

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nematocides and insecticides for their controlled

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release to soil. Coating of seeds and leaves to prevent

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Biomedical and The tissue engineering and drug delivery fields, Bodnar et al. (2007);
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Pharmaceutical ranging from skin, bone, cartilage, and vascular graft. Malafaya et al.(2007);
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For the lowering of serum cholesterol, its application Synowiecki (1986);
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in enzyme and cell immobilizations, as material for Sandford (1989).
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the production of contact lenses or eye bandages.
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Cosmetic Component of toothpaste, hand and body creams, Synowiecki (1986)
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shampoos, cosmetics and toiletries.
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Environmental In drinking water and wastewater treatment. Chitosan Gerente et al. (2007);
is used as flocculating and chelating agents, for the Guibal (2004);
removal of heavy metals and dyes, as an ecological Rinaudo (2006);
polymer (eliminates synthetic polymers and reduces Wan et al. (2004);
odours). Wu et al. (2000).
Food Industry Clarification of juices, production of biodegradable Krajewska (2005);

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packaging films, antimicrobial agents, beverage Mayer et al. (1989).

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clarification additives, flavour extenders and colour

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and texture stabilizers.
Pulp and Paper
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As a carbonless copy paper, as a processing additive Gerente et al. (2007)
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Industry for surface treatment applications, and for
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incorporation into photographic papers.

Textile Industry Inclusion of chitosan into mixtures, blends, and Gerente et al. (2007)
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coatings, of other textiles such as silk, wool, viscose,

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cotton, and others are based on chitosan¶s properties

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to repel water.
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3.0 ADSORPTION: physisorption, chemisorption or electrostatic

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Adsorption techniques are widely used to sorption.

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remove certain classes of pollutants from 3.1 Adsorption Equilibrium:

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waters, especially those that are not easily Adsorption is usually described by isotherms
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biodegradable. Adsorption is commonly
defined as the concentration of a substance at
an interface or surface. In other words
Adsorption is a process where one or more
components (adsorbates) are attracted and
bonded to the surface of a solid (adsorbent)
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which show how much solute can be adsorbed
by the adsorbent at a given temperature. An
adsorption isotherm relates the concentration
of solute on the surface of the adsorbent to the
concentration of the solute in the fluid with
which the adsorbent is in contact. These values

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with which they are in contact. The process are usually determined experimentally, but
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can occur at an interface between any two there are also models to predict them, both for
or

or

phases, such as, liquid-liquid, gas-liquid, gas- single metal adsorption and multi component
at

at

solid, or liquid-solid interfaces. The interface adsorption. Although the Langmuir and the
re

re

of interest in water and wastewater treatment Freundlich adsorption isotherms are the two
FC

FC

is the liquid-solid interface. The exact nature well established types of adsorption isotherms
of the bonding (ionic, covalent, or metallic) for single metal adsorption, there are other
D

D
tP

tP

depends on the properties of the species equations which model adsorption

involved, but the adsorbed material is equilibrium.
ar

ar

generally classified as exhibiting

m

m
.S

.S
w

w
w

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7
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ht

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 om

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.c

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Table -3: The four main classes of chitosan derivatives

or

or
at

at
A) Modified polymers: 1) Carboxymethyl chitosans 2) Alkylated chitosans

re

re
3) Chitosan sulfate derivatives 4) Carbohydrate-branched chitosans

FC

FC
5) Grafted chitosans 6)Ligand-bound chitosan

D
B) Cross linked Chitosan: 1)Covalently cross linked particles 2)Ionically cross linked particles

tP

tP
ar 3)Nano particles 4)Physical gels

ar
C) Chitosan-based composites: 1) Chitosan-dendrimer hybrids
m

m
2) Chitosan-supported on inert materials (silica gel, glass beads,
.S

.S
alumina, etc.)
w

w
w

w
D) Membranes: Chitosan Membranes from gels as a filter
w

w
Source: Harish Prashanth, K. V. and R. N. Tharanathan (2007).
://

://
tp

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ht

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Table- 4: Some methods for preparation of chitosan particles

A) Cross linking with chemicals: 1) (Single) emulsion cross linking

2) multiple emulsion
3) Precipitation/cross linking
B) Cross linking and interactions with

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charged ions, molecules and Polymers: 1) Ionotropic gelation

.c
2) Wet-phase inversion

or
3) Emulsification and ionotropic gelation
at
4) Emulsification and solvent evaporation
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5) Simple or complex coacervation (precipitation,
FC

complexation
C) Miscellaneous methods: 1)Thermal cross linking
D
tP

2) Solvent evaporation method

ar

3) Neutralization method
m

4) Spray drying
.S

5) Freeze drying
w

6) Reverse micellar
w

7) Coating
w

8) Interfacial acylation
://
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Source: Harish Prashanth, K. V. and R. N. Tharanathan (2007).

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Table -3 gives four main classes of chitosan with the movement of countless
derivatives and Table-4 outlines various droplets/particles in turbulent drying medium
methods and approaches which have been flows under changing temperature and
proposed for the preparation of chitosan humidity.
particles including microspheres/micro
om

om
particles, and nano particles. Selection of any 3.2 Adsorption Mechanisms:
.c

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of the methods depends upon factors such as The first major challenge for the adsorption
or

or

particle size requirement, thermal and field is to select the most promising types of
at

at

chemical stability. In practice, the methods are adsorbent, mainly in terms of efficiency and
re

re

often combined and different follow-up low cost. The next real challenge is to clearly
FC

FC

treatments are carried out [Krajewska B, identify the adsorption mechanism(s), in

2005]. The emulsion cross linking method is particular the interactions occurring at the
D

D
tP

tP

widely used for the synthesis of micro spheres. adsorbent/adsorbate interface. Two
With this method, the size of the particles can mechanisms are clearly established for the
ar

ar

be controlled by modifying the size of the interpretation of metal adsorption on chitosan

m

m
.S

.S

aqueous droplets. Another interesting method materials, i.e. electrostatic interactions in acid
is spray drying. This is a complex operation media (ion exchange) and metal chelation
w

w
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8
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(coordination), although the formation of ion
or
pairs has also been reported [ Guibal E., 2004,
at
Varma & Deshpande, 2002, Ravi Kumar
re
MNV.,2000, No & Meyers, 2000]. Metal ion
FC
adsorption is assumed to occur through single
or mixed mechanisms including coordination
tP
on amino groups in a pendant fashion or in
ar
combination with vicinal hydroxyl groups, and
m
ion-exchange with protonated amino groups
.S
through proton exchange or anion exchange,
w
the counter ion being exchanged with the
w
metal anion. The nature of the reaction
w
depends upon several parameters related to the
://
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adsorbent (ionic charge), to the solution (pH)
ht
and the chemistry of the metal ion (ionic
charge, ability to be hydrolyzed and to form
polynuclear species). For more details on these
mechanisms, two recent reviews can be
consulted [Guibal E., 2004, Varma &
Deshpande, 2002].
4.0. M ODELING:
Equilibrium isotherm models, adsorption
properties and equilibrium data, commonly
known as adsorption isotherms, illustrate how
pollutants interact with adsorbent materials
and so, are important in optimizing the use of
adsorbents. In order to optimize the design of
tP
an adsorption system to remove any impurity
ar
from solutions, it is important to establish the
m
most appropriate correlation for the
.S
equilibrium curve. An accurate mathematical
w
description of equilibrium adsorption capacity
w
is obligatory for reliable prediction of
w
adsorption parameters and quantitative
://
comparison of adsorption behavior for
tp
different adsorbent systems within any given
ht
system. The distribution of impurity molecule
between the liquid phase and the biosorbent is
a measure of the position of equilibrium in the
adsorption process and can generally be
expressed by one or more of a series of
isotherm models [Tien C., 1994, Langmuir I.,
om
1906, Freundlich HMF., 1906, Giles CH,
.c
Smith D, Huitson A, 1974, Giles CH, D¶Silva
or
AP, Easton IA.,1974]. The shape of an
at
isotherm may be considered with a view to
re
predicting if a sorption system is µµfavorable¶¶
FC
or µµunfavorable¶¶. The isotherm shape can
also provide qualitative information on the
D
tP
nature of the solute±surface interaction. In
ar
addition, adsorption isotherms have been
m
developed to evaluate the capacity of chitosan
.S
w
w
w
://
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ht
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materials for the adsorption of a particular
or
impurity molecule. The most popular
at
classification of adsorption isotherms of
re
solutes from aqueous solutions has been
FC
proposed by Giles et al. [Giles CH, Smith D,
D
Huitson A,1974, Giles CH, D¶Silva AP,
tP
Easton IA.,1974]. Four characteristic classes
ar
are identified, based on the configuration of
m
the initial part of the isotherm (i.e., class S, L,
.S
H, C). The subgroups relate to the behavior at
w
higher concentrations. The Langmuir class (L)
w
is the most widespread in the case of
w
adsorption of dye compounds from water, and
://
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it is characterized by an initial region, which is
ht
concave to the concentration axis. Type L also
suggests that no strong competition exists
between the adsorbate and the solvent to
occupy the adsorption sites. However, the H
class (high affinity) results from extremely
strong adsorption at very low concentrations
om
giving rise to an apparent intercept on the
ordinate. The H-type isotherms suggest the
.c
uptake of pollutants by materials through
or
chemical forces rather than physical attraction.
at
There are several isotherm models available
re
for analyzing experimental data and for
FC
describing the equilibrium of adsorption,
D
including Langmuir, Freundlich, BET, Toth,
Temkin, Redlich-Peterson, Sips, Frumkin,
Harkins-Jura, Halsey, Henderson and Dubinin-
Radushkevich isotherms. These equilibrium
isotherm equations are used to describe
experimental adsorption data. The different
equation parameters and the underlying
thermodynamic assumptions of these models
often provide insight into both the adsorption
mechanism, and the surface properties and
affinity of the adsorbent. Therefore, it is
important to establish the most appropriate
correlation of equilibrium curves to optimize
the condition for designing adsorption
systems. Various researchers have used these
isotherms to examine the importance of
om
different factors on dye molecule sorption by
.c
chitosan.
or
However, the two most frequently used
at
equations applied in solid/ liquid systems for
re
describing sorption isotherms are the
FC
Langmuir and the Freundlich models and the
most popular isotherm theory is the Langmuir
D
tP
one which is commonly used. Table- 5 reports
ar
the corresponding equations that can be used
for fitting experimental data.
.S
w
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9
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Table- 5: The two most popular equilibrium isotherm equations and their linear forms and

or

or
equation parameters

at

at
re

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Isotherm Equation Assumptions Linear form

FC

FC
D

D
Langmuir x KL Ce 1) Monolayer adsorption Ce 1 aL

tP

tP
ar qe = = 2) The sorption takes place at --- = --- + --- Ce

ar
m 1+aLCe specific sites within the Qe KL KL
m

m
adsorbent
.S

.S
3) Once a dye molecule
w

w
occupies a site
w

w
4) The adsorbent has a finite
w

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capacity for the adsorbate (at
tp

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equilibrium, a saturation
ht

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point is reached where No
further adsorption can occur)
5) All sites are identical and
energetically equivalent
6)The adsorbent is structurally
homogeneous

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Freundlich qe =KFCe1/nF 1) Multilayer adsorption 1
2)The model applies to ln qe= ln KF + ---- ln Ce

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adsorption on heterogeneous nF

or
surfaces with interaction
at
between adsorbed molecules
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3) The adsorption energy
FC

exponentially decreases on
D

completion of the sorptional

tP

centers of an adsorbent
ar

4) This is an empirical
m

equation employed to describe

.S

heterogeneous systems.
w
w
w

Source: Metcalf and Eddy 3rd edition, (1995).

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ht

4.1 Kinetic Modeling: Three kinetic models (Table 6) have been

An ideal adsorbent for wastewater pollution
control must not only have a large adsorbate
capacity but also a fast adsorption rate.
Therefore, the adsorption rate is another
important factor for the selection of the
om
widely used in the literature for adsorption
processes: (i) pseudo-first-order kinetic model
(Lagergren model) ; (ii) pseudo-second-order
kinetic model (Ho and McKay model) ; (iii)
and intraparticle diffusion model (Webber and

om
material and adsorption kinetics must be taken Morris model) .These kinetic models are used
into account since these explain how fast the to examine the controlling mechanism of
.c

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chemical reaction occurs and also provides adsorption process such significance of
or

or

information on the factors affecting the chemisorption mechanism during the

at

at

reaction rate. The kinetics of adsorption is also processes. They supposed that the
re

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another area of debate, and once again, a coordination and reaction between the dyes
FC

FC

difference in chitosan type, preparation and and the amino and hydroxy groups on chitosan
D

methodology examined makes any comparison chains would be significant and chemisorption
tP

tP

of results difficult. controlled the process.

ar

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ARTICLE IN PRE
m

m
.S

.S
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10
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Table -6: The three most popular kinetic models and their linear forms

or

or
at

at
Model Equation Linear form

re

re
Lagergren q k1 Log(qe _ qt) = logqe = k1

FC

FC
t
Log = t 2.303

D
qe-qt

tP

tP
2.303
ar

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Ho and 1/(qe-qt) = 1/qe = k2 t t/qt = 1/qc2 + 1/qe t
m

m
McKay
.S

.S
Webber and ------ Qt = ki t1/2 +c
w

w
Morris
w

w
w

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Source: Metcalf and Eddy 3rd edition, (1995).
tp

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beginning of the experiment and then
ht

Cestari et al. [Cestari et al.,2004,Dos Anjos et
al.,2002] indicated that the pseudo models did
not take into account the influence of
parameters such as temperature and kind of
dye. So, they suggested using the Avrami
model, which is the best kinetic model to
ht
controlled by intraparticle diffusion. The
adsorption system obeys the pseudo-second-
order kinetic model for the entire adsorption
period and thus supports the assumption
behind the model that the adsorption is due to
chemisorption. They also showed that the

om
evaluate multi step adsorption phenomena at kinetic parameters decreased markedly with
the solid/solution interface. However, this increasing initial dye adsorption. The

.c
model cannot give interaction mechanisms. adsorption of dye probably takes place via

or
Mass transfer involves several steps including surface exchange reactions until the surface
(i) bulk diffusion, (ii) film diffusion, (iii) at
functional sites are fully occupied; thereafter
re
intraparticle diffusion and (iv) (physical and/or dye molecules diffuse into the polymer
FC

chemical) adsorption reactions. Numerous network for further interactions and/or

D

authors consider that bulk and film diffusion reactions. Both the Lagergren, and Ho and
tP

can be ignored if a sufficient stirring speed is McKay models basically include all steps of
ar

used. This is correct for bulk diffusion but is adsorption (i.e. external film diffusion,
m

more controversial regarding film diffusion. adsorption and intraparticle diffusion), they
.S

Moreover, it is usually accepted that, in the are thus pseudo-models. However, using the
w

case of physical adsorption, the adsorption so-called pseudo-first and pseudo second-
w

itself can be considered as an instantaneous order equations for data interpretation is

w
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process, and the adsorption kinetics is questionable since the equations have no
tp

controlled either by intraparticle diffusion or physical significance. It is more reasonable to

ht

by both diffusion mechanisms at the same time
. [Tien C.,1994] .In the case of chemical
reactions, their own kinetic rates may interfere
in the control of the adsorption rate. For
complete modeling of adsorption kinetics it
would be necessary to take into accounts not
om
interpret the kinetic data in terms of mass
transfer [Crank J., 1975, Findon A. et al.,
1993, McKay G. et al., 1996].
During the past several decades, a large
number of studies of batch adsorption have
been reported in the literature and a summary

om
only the diffusion equations but also boundary of these studies can be found in the excellent
conditions including the adsorption isotherm compilation reported by Tien. Because the
.c

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equation [Guibal E., 2004, Tien C, 1994]. above two-lumped kinetic pseudo- models
or

or

This means that the system of equations is cannot identify adsorption mechanisms,
at

at

very complex but, generally, it is possible to several investigators proposed to use the
re

re

simplify the system by separating diffusion diffusion mechanisms such as intraparticle

FC

FC

steps or taking into account only diffusion diffusion using the Weber and Morris
D

steps in the control of kinetic rates. In different equation, the Avrami model and the Elovich
tP

tP

adsorption studies, the diffusion mechanisms equation [ Chang MY& Juang RS.,2005] .The
ar

ar

were considered independently in accordance former model originates from Fick¶s second
m

with the assumptions that the kinetics was law. The validity of the Elovich equation
.S

.S

controlled by external diffusion at the suggests that the chemisorption (chemical

w

w
w

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11
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reaction) mechanism is probably rate
or
controlling in the adsorption mechanism.
at
5.0 LITERATURE REVIEW:
re
Water resources, in many countries are
FC
heavily polluted by nitrate (Laigla et al.,
1990). The major concern due to nitrate is the
tP
blue-baby syndrome resulting from the
ar
conversion of hemoglobin into
m
methaemoglobin, which cannot carry oxygen
.S
(Golden and Weinstein, 1998). Nitrate,
w
contained in surface or groundwater, can be
w
removed by sorption on protonated cross-
w
linked chitosan gel beads was studied by K.
://
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Jaafari. et al., (2001).The sorption capacity is
ht
pH-dependent and large enough to meet the
standard of drinkable water. The isothermal
equilibrium curves are straight lines, which
imply that the removal is independent of the
initial concentration. If required, the sorption
capacity is easily recovered by increasing the
pH to 12. The main competitor is fluoride but,
even in its presence, the sorption capacity of
nitrate remains significant.
In conventional water treatment systems, alum
is the most widely used coagulant McLachlan
(1995) discovered that intake of large quantity
of alum salt may cause Alzheimer disease. To
minimize the detrimental effect accompanied
tP
with the use of alum, polymers are added
ar
either with alum or alone and have gradually
m
gained popularity in water treatment process.
.S
Chitosan can be a promising substitute for
w
alum in the coagulation process, because of its
w
potential feasibility in coagulation without
w
posing any health threat as the residual
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aluminium and other synthetic polymers do. In
tp
this study, Chihpin Huang et al. (1999) studied
ht
various pretreatment conditions for the
optimum chitosan modification. Batch tests
with synthetic source water suggest that the
optimal pretreatment condition to prepare
modified chitosan coagulant is deacetylation
by 45% alkali solution for 60 min, followed by
om
dissolution in 0.1% hydrochloric acid.
.c
Elvan Yilmaz and Nesrin Hasirci in (2000)
or
have studied two properties of chitosan and
at
investigated its potential as a new iron (III) ion
re
(ferric ion) adsorbing agent. In this study, the
FC
physicochemical parameters affecting the
ability of chitosan flakes to adsorb iron (III)
D
tP
ions were studied by complexmetric titration.
ar
The results showed that the iron (III)
m
adsorption capacity of chitosan increases with
.S
the amount of chitosan, degree of
w
deacetylation of chitosan, concentration of
w
w
://
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ht
om
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ferric ions in solution and with the pH of the
or
medium. The amount of ferric ions that adsorb
at
on the polymer increases with time until an
re
equilibrium is reached between adsorbed iron
FC
(III) ions and those in solution.
D
Divakaran and Pillai (2001), have studied
tP
flocculation of three freshwater algae,
ar
Spirulina, Oscillatoria and Chlorella, and one
m
brackish alga, Synechocystis, using chitosan in
.S
the pH range 4 to 9, and chlorophyll-a
w
concentrations in the range 80 to 800 mg/m3,
w
which produces a turbidity of 10 to 100
w
nephelometric turbidity units (NTU) in water.
://
tp
Chitosan reduced the algal content effectively
ht
by flocculation and settling. The flocculation
efficiency is very sensitive to pH, and reached
a maximum at pH 7.0 for the freshwater
species, but lower for the marine species.
Flocculation and settling were faster when
concentrations of chitosan higher than optimal
om
were used.
The rates of adsorption of three commercial
.c
reactive dyes and Cu (II) from water in the
or
absence and presence of complexing agents
at
using chitosan were measured by Feng-Chin
re
Wul et al., (2001). They have tested three
FC
simplified kinetic models, i.e., pseudo-first-
D
order, pseudo-second-order, and intraparticle
diffusion, to investigate the adsorption
mechanisms. It was shown that the adsorption
of reactive dyes and Cu(II) in the absence of
complexing agents could be best described by
the intraparticle diffusion model, whereas that
of Cu(II) in the absence of complexing agents
such as EDTA, citric acid, and tartaric acid by
the pseudo-second-order equation.
The design procedure for batch study has
been investigated by Gurusamy Annadurai
(2002) for Dye stuffs. The experimental results
show that chitosan is a suitable adsorbent for
adsorption of basic methylene blue.
Adsorption of 100 percentages is possible in
the higher temperature, increasing adsorbent
om
dosages and decreasing particle size ranges.
.c
They found maximum amount of dye
or
adsorption occurred at temperature level 60ƒC
at
(29 .9 mg/g); at pH level 9 .5 (29 .8 mg/g) and
re
particle size 0 .177 mm (30 .0 mg/g)
FC
S. Annouar and Mountadar et al., (2004)
studied the elimination of fluorides from
D
tP
underground water by adsorption on chitosan
ar
followed by electro dialysis with the help of
the CMX-ACS membranes. After determining
.S
the optimal conditions of the Defluoridation of
a synthetic water by the chitosan extract from
w
12
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 om
.c
the chitin of the pink shrimps, they applied it
or
to underground water of the city of
at
Youssoufia. Another application has been
re
made by electro dialysis of which the optimal
FC
conditions of treatment have been pre-
established. A comparison of the two
tP
processes was also given.
ar
Torres et el., (2004), prepared chitosan micro
m
spheres with a mean size of 140 ± 119 µm by
.S
the spray and coagulation methods. The micro
w
spheres were chemically modified using a)
w
cross linking with glutaraldehyde b) cross
w
linking with epychlorohydrin and c)
://
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acetylation. They performed adsorption
ht
experiments using a static method. The
adsorption media and equilibrium
concentration of adsorbates were varied in the
ranges of pH 4-11 and 0.07-0.70 mg.ml-1,
respectively. The maximum adsorption
capacities (qm) and the constant of the
Langmuir model (Ks) were shown to be
dependent on charge interactions and on the
kind of treatment performed on chitosan micro
spheres.
Moattar and Hayeripour (2004) have reported
two types of Shrimp Chitin derivatives and
two types of Iranian natural Zeolite derivatives
(Firuzkooh linoptiliolite) for adsorption and
tP
treatment of low-level radioactive liquid waste
ar
(LLW). Chitin with lowers than 10% and
m
Chitosan with higher than 90% deacetylation
.S
factor were selected as natural organic
w
adsorbents. They found that the adsorption
w
efficiency depend on particle size, PH,
w
adsorbent type, deacetylation factor and cation
://
type. The best Cs (Caesum) adsorption
tp
occurred in Na form Clinoptilolite. Chitin
ht
derivatives, particularly Chitosan, are more
efficient than Zeolite adsorbents for removing
of radio nuclides.
Nomanbhay (2005) prepared a new
composite biosorbent by coating chitosan onto
acid treated oil palm shell charcoal (AOPSC).
om
The adsorption capacity of the composite
.c
biosorbent was evaluated by measuring the
or
extent of adsorption of chromium metal ions
at
from water under equilibrium conditions at
re
25ºC. Using Langmuir isotherm model, the
FC
equilibrium data yielded the following
ultimate capacity values for the coated
D
tP
biosorbent on a per gram basis of chitosan:
ar
154 mg Cr/g. After the biosorbent was
m
saturated with the metal ions, the adsorbent
.S
was regenerated with 0.1 M sodium
w
hydroxide. Maximum desorption of the metal
w
w
://
tp
ht
om
.c
takes place within 5 bed volumes while
or
complete desorption occurs within 10 bed
at
volumes.
re
Rashmi Sanghi and Bani Bhattacharya
FC
(2005), were studied decolourization by
D
coagulation. For optimum results the variables
tP
studied with polyaluminium chloride (PAC)
ar
were pH, dosage and temperature. Coagulation
m
efficiencies of natural polyelectrolyte such as
.S
psyllium and chitosan alone or as coagulant
w
aids found to be very effective for the
w
decolourization of acidic and direct dyes.
w
Chitosan and other similar coagulants were
://
tp
used in the treatment of an olive oil water
ht
suspension as a model for the processing
wastewater. The effect of chitosan, starch,
alum and ferric chloride on the coagulation of
oil droplets were determined by the jar test
apparatus and turbidometric measurements. At
optimum conditions of coagulation and
om
flotation stages, the COD of the olive oil
emulsion could be reduced by 95%. (B.
.c
Meyssami et al., 2005).
or
Liu and Bai (2006) have reported their study
at
on the effect of fabrication factors influencing
re
the structures and morphologies of the
FC
chitosan and cellulose acetate blend hollow
D
fibers as adsorptive membranes to achieve
highly porous and macro voids-free structures
with different pore sizes. They found that by
increasing the alkalinity of the coagulants, the
coagulation rate of the blend hollow fibers was
increased.
Chunxiu and Renbi(2006) in their study
prepared highly porous adsorptive hollow fiber
membranes from chitosan (CS) and cellulose
acetate (CA) blend solutions. Adsorption
experiments showed that the CS/CA blend
hollow fiber membranes had good adsorption
capacity (up to 35.3±48.2 mg/g), fast
adsorption rates and short adsorption
equilibrium times (less than 20±70 min) for
copper ions, and can work effectively at low
om
copper ion concentrations (<6.5 mg/l) to
.c
reduce the residual level to as low as 0.1±0.6
or
mg/l in the solution. They found that the
at
copper ions adsorbed on the hollow fiber
re
membranes can be effectively desorbed in an
FC
EDTA solution (up to 99% desorption
efficiency) and the hollow fiber membranes
D
tP
can be reused almost without loss of the
ar
adsorption capacity for copper ions
Ahmed et al. (2006) have used Chitosan as a
.S
coagulant for oily wastewater. They compared
performance of chitosan with alum and PAC.
w
13
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 om

om
.c

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The results obtained proved that chitosan was Luigi Rizzo et.al., (2007) were compared

or

or
comparatively more efficient and economical chitosan and conventional coagulants

at

at
to alum and PAC. (aluminum sulphate and ferric chloride) in

re

re
In the study, shingling et. al.,(2006), terms of turbidity and natural organic matter

FC

FC
attempted to find a new adsorbent material (NOM) removal, as well as acute toxicity on

D
based on chitosan to improve adsorption Daphnia magna of coagulated and

tP

tP
selectivity for heavy metals, so that the cross
ar coagulated/chlorinated surface water. All

ar
linked N,O-car boxy methyl-chitosan resin coagulants decreased toxicity on D. magna
m

m
with Pb(II) as template ions (cross linked from 100% to 0% immobilization. However,
.S

.S
CMC template) were synthesized by using the addition of humic acids affected final
w

w
CMC adsorbed Pb(II) ions cross linked with toxicity in different ways according to
w

w
glutaraldehyde. The adsorption experiments coagulant type and dose.
w

w
demonstrated the cross linked CMC template Yimin Qin et.al, (2007), examined the
://

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tp

tp
has high adsorption selectivity for Pb (II) ions combined use of chitosan and sodium alginate
ht

in solution containing single metal ions or
coexistence of three metals ions of Cu(II),
Zn(II)and Pb(II). They also investigated that
the cross linked CMC template has a good
reusability and stability as compared to CMC.
Fung Hwa et al., (2006) studied the
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in the treatment of wastewater containing
heavy-metal ions and dye. They found that
when used in combination, sodium alginate
and chitosan were effective in removing
copper, cadmium, lead, and silver ions as well
as acid dye molecules.

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suitability of chitosan to treat the wastewater Antonio R. Cestari et al., (2008) used a
from milk processing plant. Chitosan is a factorial design to evaluate the quantitative

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natural material, the sludge cake from the removal of an anionic red dye from aqueous

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coagulation after dehydrated could be used solutions on epichlorohydrin-cross-linked
directly as feed supplement, therefore not only at
chitosan. The results indicated that increasing
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saving the spent on waste disposal but also the dye concentration from25 to 600mg/L
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recycling useful material. The result shows increases the dye adsorption. The factorial
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that the optimal result was reached under the results also demonstrate the existence of
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condition of pH 7 with the coagulant dosage of statistically significant binary interactions of

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25 mg/l. The analysis of cost-effective shows the experimental factors.

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that no extra cost to use chitosan as coagulant The cross linked chitosan synthesized by the
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in the wastewater treatment, and it is an homogeneous reaction of chitosan in aqueous

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expanded application for chitosan. acetic acid solution with epichlorohydrin were
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The arsenic speciation and arsenic removal in used to investigate the adsorptions of three
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chitosan packed column were studied by metals of Cu(II), Zn(II), and Pb(II) ions in an
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Martha Benavente et al., (2006). They found aqueous solution. Arh-Hwang Chen et al.,
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that arsenic adsorption depends mainly on the (2008) in their study found that the adsorption
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pH as well as the activity of functional groups
that compose the chitosan structure. At pH 3
and volume of adsorbent material of 337.8 cm3
an adsorption of 94% was obtained from
arsenic standard solution.
Jian Ping Wang et al., (2007), used chitosan-
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process was followed the second-order kinetic
equation. The order of adsorption capacity for
three metal ions follows: Cu2+ >Pb2+ >Zn2+.
The results obtained from the equilibrium
isotherms adsorption studies well fitted to the
Langmuir isotherm equation under the

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g-PDMC (poly (2-methacryloyloxyethyl) concentration range studied.
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trimethyl ammonium chloride), as coagulant to Baohong Guan et al., (2008) have studied the
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treat a paper-recycling wastewater with removal of Heavy metals Mn(II) and Zn(II)
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aluminum chloride. The optimal conditions from wastewater with water-soluble chitosan.
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obtained from the compromise of the two The results showed that compared with the
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desirable responses, turbidity and SVI, were settling of metal hydroxide, the chitosan±metal
coagulant dosage of 759 mg/l, flocculent complex had better separating performance.
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dosage of 22.3 mg/l and pH 5.4, respectively. Application of chitosan solution for chelation
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The RSM was demonstrated as an appropriate could remove Mn(II) and Zn(II) efficiently and
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approach for the optimization of the make it easy to separate sediment from dual-
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coagulation±flocculation process by alkali FGD wastewater.

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confirmation experiments.
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Decontamination of lead ions from aqueous specifically photo catalysis (PC), Fenton (F)

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media has been investigated using cross linked and photo-Fenton (PF), was investigated by

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xanthated chitosan (CMC) as an adsorbent by Luigi Rizzo et al.,(2008). The optimum

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Divya Chauhan and Nalini removal of total suspended solids (TSS, 81%)

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Sankararamakrishnan (2008). Maximum by chitosan coagulation was achieved at actual

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adsorption was observed at both pH 4 and 5. pH (4.3) for 400mg/l coagulant dose. The

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The adsorption data followed both Freundlich
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and Langmuir isotherms. and PF (95%) processes were achieved after
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Droppo et al., (2008) studied behavior of 2.0 and 1.0 h, respectively by using
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Hamilton Barbour sediments mixed with three 15,000/1852 (w/w) ratio of H2O2/FeSO4.
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different amendments: alum, chitosan (both The applicability of neodymium-modified
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coagulants) and a polyacrylamide (a chitosan as adsorbents for the removal of
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flocculant). Results show that amendment excess fluoride ions from water was studied by
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addition is an effective method for the Ruihua Yao et al.,(2008). The equilibrium
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management of high turbidity. Floc formed
with chitosan has high settling value.
The removal of arsenic (As) species, such as
As(III) and As(V), from water by molybdate-
impregnated chitosan beads (M ICB) in both
batch and continuous operations was studied
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sorption data were fitted reasonably well for
Langmuir isotherm model, the maximum
equilibrium sorption had found to be11.411±
22.380mg/g.
Vandana Singh et al.,(2008) in their study
reported the effect of optimization of

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by Chih-Yu Chen et al.,(2008). The results persulfate/ascorbic acid initiated synthesis of
indicated that MICB favor the adsorption of chitosan-graft-poly (acrylamide) (Ch-g-PAM)

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both As(V) and As(III). The optimal pH value and its application in the removal of azo dyes.

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for As(III) and As(V) removal was 5. The The Ch-g-PAM was found to be very efficient
adsorption of arsenic on the MICB is most at
in removing color from real industrial
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likely an exothermic reaction. The optimal wastewater. The adsorption data of the Ch-g-
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desorption solution for arsenic recovery was 1 PAM and Ch for both the dyes were modeled
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M H2SO4, which resulted in a 95% efficiency by Langmuir and Freundlich isotherms where
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for As(III) and 99% for As(V). the data fitted better to Langmuir isotherms.
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Batch adsorption experiments were carried Both Ch-g-PAM and Ch followed pseudo-
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out for the removal of methylene blue (MB) second-order adsorption kinetics. The
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cationic dye from its aqueous solution using thermodynamic study revealed a positive heat
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chitosan-g-poly (acrylic acid)/montmorillonite of adsorption indicating spontaneous and

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nano composites as adsorbent. In this study Li endothermic nature of the adsorption.

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Wang et al., (2008) showed that the nano The effect of chitosan immobilization of
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composites have great influence on adsorption Scenedesmus spp. cells on its viability, growth
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capacities and introducing a small amount of and nitrate and phosphate uptake was
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MMT could improve adsorption ability. The
adsorption behaviors of the nano composite
showed that the adsorption kinetics and
isotherms were in good agreement with
pseudo-second-order equation and the
Langmuir equation, respectively, and the
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investigated by Sashenka Fierro et al.,(2008).
Scenedesmus sp. (strains 1 and 2) and
Scenedesmus obliquus immobilized in
chitosan beads showed high viability after the
immobilization process. Immobilized cells
accomplished a 70% nitrate and 94%

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maximum adsorption capacity is 1859 mg/g. phosphate removal within 12 h of incubation
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Ona Gyliene et al.,(2008) studied the use of Sirlei Rosa et al.,(2008) studied the use of
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biosorbent chitosan to remove both heavy adsorption of reactive orange 16 by quaternary

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metals and organic compounds from fresh chitosan salt (QCS) to remove reactive dyes
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water. They found, the essential from textile effluents. The results obtained
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microelements calcium and magnesium are not demonstrate that the adsorbent material could
removed from water after the treatment with be utilized to remove dyes from textile
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chitosan effluents independent of the pH of the aqueous

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In work the combined pre-treatment of actual medium.

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olive mill wastewaters by coagulation with Suparna Dutta et al.,(2008) have done a
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natural organic coagulant, such as chitosan, comparative study between the two radiation
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and the advanced oxidation processes, grafted chitosan derivatives viz. cross-linked
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chitosan (CRC) and cross-linked chitosan after behavior that had its Langmuir character

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hydrolysis (CRCH). It was seen that CRCH increased as the pH was increased.

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had a greater uptake of metal ions compared to Investigation was carried out by E. Biro et

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CRC but CRC was more selective of the two. al., (2009) to elucidate the influence of process

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Sudipta Chatterjee & Seung Han Woo (2008) parameters on the mean particle size of

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has done a physico-chemical investigation of chitosan micro spheres produced by water-in-

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the adsorption of nitrate by chitosan hydro
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beads. The maximum adsorption capacity was found that model equation proved to be
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found to be 92.1 mg/g at 30oC. The kinetic suitable for the prediction of the mean particle
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result corresponds with the pseudo-second- size as a function of the studied process
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order rate equation. They found adsorption parameters.
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process is a spontaneous, exothermic process The removal of a reactive (Remazol Yellow
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and has positive entropy. Desorption of nitrate Gelb 3RS) and a basic (Basic Yellow 37) dye
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from the loaded beads was accomplished by from aqueous solutions was investigated by
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increasing the pH of the solution to the
alkaline range, and desorption ratio of 87%
was achieved at pH 12.0.
Tania Chatterjee et al., (2008) showed the
optimum concentration of chitosan required
for maximum coagulation of bentonite
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George Z. Kyzas et al., (2009) using cross-
linked chitosan derivatives as sorbents (either
powder or beads), which have been grafted
with carboxyl and amide groups. Chitosan
powder presented higher sorption capacity
than beads. Chitosan grafted with amide

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suspension was 5 mg/l. They used five groups was found superior sorbent for reactive
additive for conditioning, NaHSO4, at all dye at pH 2 (Qmax = 1211 mg/g), while

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concentrations, was found to be the most chitosan grafted with carboxyl groups for

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effective for enhancing the coagulating basic dye at pH 10 (Qmax = 595 mg/g).
efficiency of chitosan and it was at its at
A new biosorbent was developed (Srinivasa
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maximum when conditioned by 0.05M R. Popuri et al., 2009) by coating chitosan on
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NaHSO4. NaHSO4 conditioned chitosan to polyvinyl chloride (PVC) beads. The

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showed better coagulating efficiency than biosorbent was characterized by FTIR spectra,
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unconditioned chitosan at all pH. Using 5 mg/l porosity and surface area analyses. The
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of NaHSO4 conditioned chitosan at pH 6, the experimental data were fitted to Langmuir and
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removal percentage of bentonite was increased Freundlich adsorption isotherms. The

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from 76% to 88 % compared to unconditioned maximum monolayer adsorption capacity of

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chitosan. chitosan coated PVC sorbent as obtained from

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Wan Ngah W.S. & Fatinathan (2008) found Langmuir adsorption isotherm was found to be
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use of chitosan beads, chitosan±GLA beads, 87.9 mg/ g for Cu(II) and 120.5 mg/ g for
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and chitosan±alginate beads were very Ni(II) ions, respectively.

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effective for the removal of Cu(II) ions from

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aqueous solution at different initial pH, 6.0 ECONOMIC ASPECTS:

agitation periods, adsorbent dosage, and initial Ɣ Many Researchers have mainly focused on
concentrations. Chitosan±alginate beads the technical performances of chitin, chitosan
showed a better fit to the non-linear Langmuir and its derivatives, while their economic
isotherm giving an adsorption capacity of aspect is usually neglected. Cost is actually an
67.66 mg/g. important parameter for comparing adsorbent
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Wen F. Sye et al.,(2008) described a new materials. According to Bailey et al. [Bailey
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method for the removal of colour from textile SE, Olin TJ, Bricka M, Adrian DD.,1999] a
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wastewater. They used porous crab shell and sorbent can be considered low cost if it
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chitosan beads as adsorbents for removal of requires little processing, is abundant in

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water-soluble dyes present in textile dyeing nature, or is a by-product or waste material

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wastewater. from another industry.

In the work, W. A. Morais et al.,(2008) Ɣ Chitosan-based materials exhibit economic
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analyzed the sorption of a model dye, methyl advantages:

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orange, on chitosan hydro beads is in terms of Chitin is a material obtained from natural raw
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equilibrium and kinetic approaches. resources. It is only commercially extracted

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Equilibrium studies showed that dye from crustaceans which are conveniently
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adsorption had a mixed Freundlich±Langmuir available as waste from processing shellfish.

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The wastes consists of chitin (20±30%), not the same, logically. The following

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proteins (20±40%), salts (mainly carbonate conclusions may be made:

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and phosphate, 30±60%) and lipids (0±14%) ƔThe works reviewed above indicate that bio-

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[Agullo E, Rodriguez M S, Ramos V, adsorption onto chitosan is becoming a

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Albertengo L., 2003]. These proportions vary promising alternative to replace conventional

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with species and season. Several countries adsorbents used in water and wastewater

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possess arlarge unexploited crustacean Engineering for adsorption of various

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resources, especially in Asia. impurities.
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Ɣ Chitin and chitosan are now produced ƔExcellent progress has been made,
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commercially at low cost and their production representing the application of chitosan and
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is also economically interesting, especially if it cross linked chitosan in bio-adsorption of
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includes the recovery of carotenoids. A fluoride, arsenic and many of the heavy
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prerequisite for the greater use of chitin in metals. These materials are efficient in
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industry is cheap manufacturing processes removal of above mentioned impurities with
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and/or the development of profitable processes
to recover chitin and byproducts such as
proteins and pigments. It is important to note
that the recovery of these products from waste
is an additional source of revenue Crustacean
shells contains considerable quantities of
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the additional advantage of being cheap, non-
toxic and biocompatible.
ƔChitosan is characterized for its easy
dissolution in many dilute mineral acids, with
the remarkable exception of sulfuric acid.
Several methods have been developed to

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carotenoids which so far have not been reinforce chitosan stability. The advantage of
synthesized, and which are marketed as a fish chitosan over other polysaccharides is that its

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food additive in aquaculture, mainly for polymeric structure allows specific

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salmon.[ Ravi Kumar MNV.,2004] In modifications without too many difficulties.
addition, calcium carbonate which is another at
Ɣ It has the physico-chemical characteristics of
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major component of crab shells is converted to both coagulants and flocculants, i.e. high
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calcium oxide and sodium carbonate .[ Peter cationic charge density and long polymer
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MG.,1995] Pigments may be also recovered as chains, leading to bridging of aggregates and
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high value side products. precipitation. Numerous works have

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Ɣ The production of the chitosan-based demonstrated that chitosan and its derivatives
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materials is economically possible because (in particular grafted biopolymers) can be a

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they are easy to prepare with relatively potential substitute for metallic salts and
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inexpensive chemical reagents under mild synthetic polyelectrolytes in the treatment of

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conditions. The conventional method of water and wastewater for the removal of both
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extraction creates its own environmental particulate and dissolved substances.

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problems as it generates large quantities of Ɣ Several authors concluded that the binding
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concentrated effluent containing polluting was a chemisorption reaction and the

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bases and degradation products and presenting
inconsistent physicochemical properties.
Ɣ Chitosan possesses several intrinsic
properties such as its non-toxicity, its
biodegradability and its outstanding chelation
behaviour that make it an effective coagulant
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adsorption phenomenon mainly depended on
the interactions between the surface of the
adsorbent and the adsorbed species. However,
all the studies arrive at contrasting conclusions
showing the difficulty of using simple models
for the interpretation of the interactions of

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and/or flocculant for the removal of these polymeric materials with metal ions.
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contaminants in the dissolved state. Much work is necessary to clearly demonstrate

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the adsorption mechanism for the different

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7.0 CONCLUDING REMARKS: types of chitosan-based materials.

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The state-of-the-art advancement in the field Ɣ Researchers have demonstrated that chitosan
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of biosorption by Chitosan using batch and its derivatives (in particular grafted
systems is reviewed in this paper, based on a biopolymers) can be a potential substitute for
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significant number of references published in metallic salts and synthetic polyelectrolytes in

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recent times. Evidently, it is very difficult task the treatment of wastewater for the removal of
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to make a comparison of data obtained using both particulate and dissolved substances.
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different materials. The experimental However, more studies are required to refine
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conditions used by various researchers also are the optimization of the properties of chitosan
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such as the degree of deacetylation which can
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influence coagulation and the molecular
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weight which affects flocculation.
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Ɣ Various authors studied either one or at the
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max two metals salts in their study. Much
work is necessary to clearly demonstrate the
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if more than three-four different of metal salts
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are present in water /wastewater.
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