European Polymer Journal 45 (2009) 13371348

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European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Review article

Chitosan for coagulation/occulation processes An eco-friendly approach

F. Renault, B. Sancey, P.-M. Badot, G. Crini *
Universit de Franche-Comt, Laboratoire Chrono-environnement, UMR 6249 UFC/CNRS usc INRA, Place Leclerc 25030 Besanon cedex, France

a r t i c l e

i n f o

Article history:
Received 30 October 2008
Received in revised form 11 December 2008
Accepted 17 December 2008
Available online 25 December 2008

Keywords:
Biopolymer
Chitosan
Coagulation
Flocculation
Wastewater treatment
Bioocculant

a b s t r a c t
Chitosan is a partially deacetylated polymer obtained from the alkaline deacetylation of
chitin, a biopolymer extracted from shellsh sources. Chitosan exhibits a variety of physico-chemical and biological properties resulting in numerous applications in elds such
as cosmetics, biomedical engineering, pharmaceuticals, ophthalmology, biotechnology,
agriculture, textiles, oenology, food processing and nutrition. This amino-biopolymer has
also received a great deal of attention in the last decades in water treatment processes
for the removal of particulate and dissolved contaminants. In particular, the development
of chitosan-based materials as useful coagulants and occulants is an expanding eld in
the area of water and wastewater treatment. Their coagulation and occulation properties
can be used to remove particulate inorganic or organic suspensions, and also dissolved
organic substances. This paper gives an overview of the main results obtained in the treatment of various suspensions and solutions. The effects of the characteristics of the chitosan
used and the conditions in solution on the coagulation/occulation performance are also
discussed.
2008 Elsevier Ltd. All rights reserved.

Contents
1.
2.
3.

4.
5.
6.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Categories of materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Why use coagulants and flocculants based on biopolymers? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.1. Coagulation/flocculation process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Chitosan as bioflocculant . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Mechanisms of coagulation/flocculation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Chitosan for coagulation and flocculation a review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
Conclusions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1. Introduction
Water pollution results from all Human activities:
domestic, industrial and agricultural, and is not only due
to petroleum, minerals, sewage treatment sludge or persistent organic pollutants produced by the incineration of
* Corresponding author. Tel.: +33 3 81 66 57 01; fax: +33 3 81 66 57 97.
E-mail address: gregorio.crini@univ-fcomte.fr (G. Crini).
0014-3057/$ - see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.eurpolymj.2008.12.027

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waste, but also to synthetic substances produced by chemistry (dyes, fertilisers, pesticides, and so on) [1]. When
water is polluted, decontamination becomes necessary.
The best purication approach are sought to reach the
decontamination objectives required by law. The literature
reports a multitude of processes for the decontamination
of contaminated water and wastewater such as coagulation, precipitation, extraction, evaporation, adsorption on
activated carbon, ion-exchange, oxidation and advanced

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F. Renault et al. / European Polymer Journal 45 (2009) 13371348

oxidation, incineration, electrooatation, electrochemical

treatment, biodegradation and membrane ltration [27].
However, many of the available processes proposed cannot
be used on an industrial scale for technological and especially economic reasons. Complete treatment will clearly
require several steps and it is often appropriate to combine
several methods of purication before maximal efciency
is obtained, knowing that each method has its advantages
and its disadvantages. An industrial efuent treatment
process line must also be designed according to the quality
objectives: for instance lowering the levels of pollution, return to a watercourse or recycling.
A general scheme of industrial water treatment involves
three main stages [1]:
a primary treatment or pre-treatment step using
mechanical, physical and chemical methods;
a secondary treatment or purication step using chemical or biological methods;
and treatment of the sludge formed (incineration for
example).
In certain cases, a tertiary treatment of the water can
also be required to remove the remaining pollutants or
the molecules produced during the secondary purication
(e.g., the removal of salts produced by the mineralisation of
organic matter). Primary treatment only concerns heterogeneous efuent, i.e., efuent containing suspended solids
or immiscible liquids, and eliminates the solid particles
and suspended substances (colloids or dispersions) from
the efuent. This pre-treatment stage is mandatory before
secondary treatment because otherwise particulate pollution would hinder later treatment, make it less efcient
or damage the purication equipment.
Coagulation/occulation is a frequently applied process
in the primary purication of industrial wastewater (and in
some cases in secondary and tertiary treatment) [815].
Coagulation using chemical coagulants consists of combining insoluble particles and/or dissolved organic matter into
large aggregates, thereby facilitating their removal in subsequent sedimentation, oatation and ltration stages. It
usually involves the dispersal of one or several chemical
reagents which destabilises the colloidal particles, leading
to the formation of micro-oc. Bonding the micro-oc particles together by the addition of a occulation additive
forms larger, denser akes that are easier to separate. A
simple separation step then eliminates the oc. The coagulants and occulants frequently used are mineral additives
including metal salts such as polyaluminium chloride and
synthetic polymers such as polyacrylamide. Using these
chemical substances may have several environmental consequences (i) an increase in metal concentration in water
(which may have human health implications); (ii) production of large volumes of (toxic) sludge; (iii) dispersion of
acrylamide oligomers which may also be a health hazard.
For these reasons, alternative coagulants and occulants
have been considered for environmental applications
[1622]. Biopolymers may be of great interest since they
are natural low-cost products, characterized by their environmentally friendly behaviour. Among these biopolymers,
chitosan may be considered as one of the most promising
coagulation/occulation materials [17].

2. Categories of materials
The use of organic polyelectrolytes in water treatment
was recently reviewed by Bolto and Gregory [16], with
emphasis on the types of polymers commonly available
and the nature of the impurities to be removed. Polyelectrolyte applications in industrial wastewater treatment
have been reviewed by Bratby [17] and Trkman [22].
Examples include efuents from the dye, textile and milk
industries.
There are two major classes of materials used in coagulation/occulation processes [11,17]:
(1) inorganic and organic coagulants including mineral
additives (lime, calcium salts, etc.), hydrolysing
metal salts (aluminium sulphate, ferric chloride, ferric sulphate, etc.), pre-hydrolysed metals (polyaluminium chloride, polyaluminosilicate sulphate,
etc.) and polyelectrolytes (coagulant aids);
(2) and organic occulants including cationic and anionic polyelectrolytes, non-ionic polymers, amphoteric and hydrophobically modied polymers, and
naturally occurring occulants (starch derivatives,
guar gums, tannins, alginates, etc.).
Coagulation is mainly induced by inorganic metal salts,
e.g., aluminium and ferric sulphates and chlorides. The
most common additives are aluminium sulphate (generally known as alum), ferric chloride and ferric sulphate
[11,17]. The addition of these cations results in colloidal
destabilization, as they specically interact with and neutralise the negatively charged colloids. For example, once
the Fe(III) coagulant has been added to the solution to be
treated, the Fe(III) ions hydrolyse rapidly in an uncontrollable manner, forming a range of hydrolysis species which
play an essential role in the coagulation process. Metal
speciation in solution has been well documented [11,17].
In wastewater treatment using inorganic coagulants, an
optimum pH range in which metal hydroxide precipitates
occur, should be determined. The addition of metals depresses the wastewater pH to a lower value. In general,
decreasing the pH from the alkaline levels to near neutral
levels has a strong positive effect on the reduction of turbidity, suspended solids (SS) and chemical oxygen demand
(COD). However, the signicant disadvantage of these conventional coagulants is the inability to control the nature
of the hydrolysis species formed when the coagulant is
introduced in the solution [17]. As a result, their performance is dependent not only on the pH of the water and
their concentration, but also on the temperature and nature of the solution. Therefore, new types of reagents have
been developed [11,23]. Alternative coagulants based on
pre-hydrolysed forms of aluminium (such as polyaluminium chloride or PAC) and iron (polyferric sulfate or PFS) are
more effective than the traditional additives. Their signicant advantage is that their hydrolysis occurs under specic experimental conditions during the preparation
stage of the coagulants, and not after their addition to
the raw solution. This results in a much tighter control of
the procedure. It is known that PAC-based products provide better coagulation than alum at low temperatures

F. Renault et al. / European Polymer Journal 45 (2009) 13371348

and also produce lower volumes of sludge. Because they

are already partially neutralised, they have less effect on
the pH of the water and so reduce the need for pH correction. However, a detailed understanding of the occulation
mechanisms (in particular the mode of action) of these
coagulants is still lacking [11,16,17,22].
The coagulation process is not always perfect as it may
result in small ocs when coagulation takes place at low
temperatures or produce fragile ocs which break up when
subjected to physical forces. It is not only necessary to
overcome these problems but also to improve the process
to obtain good quality efuent and rapid sedimentation of
the ocs formed. To do so, several products known as coagulant aids or polymeric additives can be used to bring
together and agglomerate the ocs formed by the coagulant [11,17]. These water-soluble polymers, regularly used
in water treatment, are mainly synthetic, although a few
natural products may be of interest [16,20,21]. The polymeric additives are broadly characterized by their ionic
structure: cationic, anionic and non-ionic [20,21]. Ionic
polymers or polyelectrolytes of various structures are
usually used as coagulant aids to enhance the formation
of larger oc in order to improve the rate of sedimentation
[17,22]. Coagulant aids can act either by polymer bridging
or by charge neutralization [11,17,20,21].
Flocculants are used in fast solidliquid separations
involving the aggregation of particles. Flocculating agents
are classied into inorganic and polymeric materials
[11,17]. Inorganic occulants have almost been abandoned
because they had numerous disadvantages such as the large
amounts required for efcient occulation and subsequently the large volume of sludge produced. They are also
highly sensitive to pH, inefcient towards very ne particles, and applicable only to a few disperse systems [17,22].
As mentioned, inorganic polymeric occulants such as
pre-hydrolysed PFS or polyferric chloride (PFC) have been
recently proposed. These materials contain complex polynuclear ions formed by OH bridging having high molecular
weight and high cationic charge. These compounds become
more effective at a comparatively lower dose than the conventionally applied reagents. They can be used over a wide
range of pH and temperature due to their high level of
hydrolysis.
Technological progress in polymer chemistry has also
improved occulant technology to provide organic polymers and polyelectrolytes with greater purication efciency [16,24,25]. Commercial organic occulants are
basically of two types: synthetic materials based on various
monomers (acrylamide, acrylic acid, diallyldimethylammonium chloride, etc.) and natural organic materials based on
polysaccharides or natural polymers (starch, cellulose,
alginate, natural gums, etc.) [2628]. The advantage of polymeric occulants is their ability to produce large, dense,
compact ocs that are stronger and have good settling characteristics compared to those obtained by coagulation.
Polymeric occulants are easy to handle and immediately
soluble in aqueous systems. They can also reduce the sludge
volume. Because cationic polymeric occulants destabilize
particles and colouring matter through the compression of
electrical double layers, charge neutralization, adsorption
and subsequent formation of particlepolymerparticle

1339

bridges, high removal efciency can be achieved even with

a small amount of occulant, which generates a small volume of sludge [11]. Furthermore, the polymer performance
is less dependent on pH (for example polyamines are effective over a wide range of pH). There are no residuals or
metals added such as Al(III) and Fe(III), and the alkalinity
is maintained. The occulation performance primarily depends on the type of occulant used, how much is used,
its molecular weight, ionic nature, the type of material in
suspension wastewater and the type of wastewater
[11,1522]. Table 1 shows some examples of commercial
polymeric occulants. For example, poly(acrylamide)
(PAM) is a commonly used organic polymeric occulant because it is possible to synthesize polymers with various
functions (positive, negative or neutral charge) which can
be used to produce a good settling performance at relatively
low cost. Although extensive work has been done, future
research needs to look into how molecular weight and
charge density distribution affect the occulation performance to produce a better choice of occulants for specic
industrial applications [11,17,22].
3. Why use coagulants and occulants based on
biopolymers?
3.1. Coagulation/occulation process
As previously reported, the inorganic salt aluminium
sulphate (alum) is one of the most widely used coagulants
in conventional water and wastewater treatments. The
performance of alum no longer needs to be proved and is
appreciated for its low cost, ease of use and availability.
However, it produces abundant sludge that is difcult to
dehydrate, its efciency is entirely dependent on the pH
and when formed in cold water alum ocs are not very
mechanically resistant. In addition, the use of alum is a
source of concern and the debate about its possible toxicity
is still open. Since high aluminium concentrations in water
may have human health implications, environmentally

Table 1
Examples of polymeric occulants used in water and wastewater
treatment.
Cationic polyelectrolytes
 Poly(diallyldimethyl ammonium chloride)
 Epichlorohydrin/dimethylamine polymers
 Cationic polyacrylamides
 Poly(alkylamines) [poly(ethyleneimine), poly(vinylamine)]
 Poly(styrene) derivatives
 Ionenes
 Sulphonium polymers
 Natural cationic polymers (chitosan, cationic starches)
Anionic polyelectrolytes
 Anionic polyacrylamides
 Carboxylic acid polymers
 Phosphonic acid polymers
 Sulphonic acid polymers
 Natural anionic polymers (sulphated polysaccharides, modied
lignin sulphonates)
Non-ionic polymers
 Polyacrylamide
 Natural non-ionic polymers (starch, cellulose derivatives)

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F. Renault et al. / European Polymer Journal 45 (2009) 13371348

friendly coagulants will present an interesting alternative

for the purication of wastewaters [17]. The use of inorganic polymeric coagulants has been also questioned.
Increasing use is also being made of synthetic coagulants of organic polymeric origin. Commercial synthetic
polymers have been utilised in coagulation/occulation
processes for water purication for at least four decades
[11,16,17]. In comparison with alum, some of the advantages of these polymers are: lower coagulant dose requirements, increase in the rate of separating the solid and
water phases arising from larger agglomerate sizes, efciency at low temperatures (hydrolysing metal coagulants
perform less well at low temperatures), a smaller volume
of sludge, a smaller increase in the ionic load of the treated
water, a less pH-dependent process and a reduced level of
aluminium in the treated water. Polymer-based products
also improve settleability and increase the oc toughness.
However, although synthetic water-soluble polymers nd
a wide range of applications as coagulants and occulants,
the potential problems associated with their use are high
cost, lack of biodegradability and polymer toxicity. It is
important to note that the use of polyelectrolytes is also
a source of debate. Contaminants of synthetic polymers
used in water and wastewater treatment generally arise
from residual unreacted monomers (such as acrylamide,
ethyleneimine, and trimethylolmelamine), unreacted
chemicals used to produce the monomer units (such as
epichlorohydrin, formaldehyde and dimethylamine) and
reaction by-products of the polymers in water [11,16,17].
For example, acrylamide is extremely toxic producing severe neurotoxic effects [17]. Commercial forms of synthetic organic occulants may also contain toxic products
from the additives. Bolto and Gregory [16] reported that
the normally used anionic and non-ionic polymers are generally of low toxicity, but cationic polyelectrolytes are
more toxic, especially to aquatic organisms. The majority
of commercial polymers are also derived from petroleum-based raw materials using processing chemistry that
is not always safe or environmentally friendly. Today, there
is growing interest in developing natural low-cost alternatives to synthetic polyelectrolytes [2931]. Numerous
biological products have recently been proposed and studied as effective coagulants and occulants for replacing
conventional materials [3236]. Some of the reported
products named bioocculants include biopolymers
(starches, chitosan, alginates) and microbial materials produced by micro-organisms including bacteria, fungi and
yeast [37]. Compared with conventional chemical occulants, bioocculants are safe and biodegradable polymers,
and produce no secondary pollution [17,30,31,38,39]. They
may potentially be applied not only in food and fermentation processes, downstream processing but also in water
and wastewater treatment. Because of the above concerns
on polyelectrolyte toxicity, it is believed that the use of
bioocculants will increase [17,30,39].
Over the usual range of water pH (59) particles
nearly always carry a negative surface charge and because
of this, are often colloidally stable and resistant to aggregation. Coagulants are then needed to destabilise the particles. Destabilisation can be brought about by either
increasing the ionic strength (giving some reduction in

the zeta potential and a decreased thickness of the diffuse

part of the electrical double layer) or specically adsorbing
counterions to neutralise the particle charge. It is well
known that bioocculants can play these roles because
they have particular macromolecular structures with a
variety of functional groups which can interact with contaminants [30,31]. Bioocculation is a novel approach that
is effective and competitive. In particular, chitosan is a
promising bioocculant for environmental and purication
purposes, as reported in recent patents [3942].
3.2. Chitosan as bioocculant
Chitosan is a linear copolymer of D-glucosamine and Nacetyl-D-glucosamine produced by the deacetylation of
chitin, a natural polymer of major importance [43,44]. Chitin is the second most abundant biopolymer in the world,
after cellulose. The main sources exploited are two marine
crustaceans, shrimps and crabs. Chitosan has unique properties among biopolymers especially due to the presence of
primary amino groups and it is a commercially interesting
compound because of its high nitrogen content in comparison to cellulose [43]. The main parameters inuencing the
characteristics and properties of chitosan are its molecular
weight (MW), degree of deacetylation (DD), representing
the molar fraction of deacetylated units, and crystallinity.
These parameters are determined by the conditions set
during preparation [44,45].
The potential industrial use of chitosan is widely recognized. This versatile material is used in biomedical
engineering, pharmacy, dentistry, ophthalmology, biotechnology, chemistry, cosmetics, textile, pulp and paper,
oenology, food industry, agriculture and photography
[4652]. Chitosan is also widely applied in water and
wastewater treatment (Table 2) because it can be conditioned and used for pollutant complexation in different
forms, from water soluble forms to solid forms (gels, beads,

Table 2
Principal properties of chitosan in relation to its use in water and waste
treatment application.
Principal characteristics

Potential applications

 Non-toxic

 Flocculant to clarify water

(drinking water, pools)
 Reduction of turbidity in food
processing efuents
 Coagulation of suspended solids,
mineral and organic suspensions
 Flocculation of bacterial
suspensions

 Biodegradable
 Renewable resource
 Ecologically acceptable polymer
(eliminating synthetic polymers,
environmentally friendly)
 Efcient against bacteria, viruses,
fungi
 Formation of salts with organic
and inorganic acids
 Ability to form hydrogen bonds
intermolecularly
 Ability to encapsulate
 Removal of pollutants with
outstanding pollutant-binding
capacities

 Interactions with negatively

charged molecules
 Recovery of valuable products
(proteins. . .)
 Chelation of metal ions
 Removal of dye molecules by
adsorption processes
 Reduction of odours
 Sludge treatment
 Filtration and separation
 Polymer assisted ultraltration

F. Renault et al. / European Polymer Journal 45 (2009) 13371348

membranes, bers, etc.). Chitosan has been used in the solid state for the chelation of metal ions in near-neutral
solution, the complexation of metal anions in acidic solution and the dye complexation using adsorption processes
[5357]. This biopolymer has been used in gel-bead form
for adsorption in batch or xed-bed column systems,
deposited on a suitable support (e.g., ceramic), or in a
water soluble form in polymer-enhanced ultraltration
processes and solvent extraction processes [5762].
Chitosan also possesses several intrinsic characteristics
that make it an effective coagulant and/or occulant for the
removal of contaminants in the dissolved state [57,59]. It
has characteristics of both coagulants and occulants, i.e.,
high cationic charge density, long polymer chains, bridging
of aggregates and precipitation (in neutral or alkaline pH
conditions). Its uses are justied by two important advantages: rstly, its non-toxicity and biodegradability [17];
secondly its outstanding chelation behaviour [53,55,56].
Its unique physico-chemical properties render it very efcient in interactions with various contaminants including
both particulate and dissolved substances. These properties have been exploited for the design of coagulation/occulation processes applied to the treatment of various
efuents (see Table 3). For example, chitosan has been successfully used, for precipitative occulation at pH above
the pKa of the macromolecule, in the treatment of mineral
and organic suspensions [7375] and the coagulation of
negatively charged contaminants in acidic solutions containing dyes [85] or humic acid [82,83]. Other examples
can be found in the review of No and Meyers [57].
The main reasons for the success of biopolymers such as
chitosan in wastewater treatment using coagulation/occulation processes are: chitosan has the advantage of being
a non-toxic material, non corrosive and safe to handle well
(non hazardous product, not irritating for skin and eyes. . .)
[16,17]; Hirohara et al. patented a chitosan-based material
safe to animals and plants without causing environmental
pollution [39]; chitosan is efcient in cold water and at
much lower concentrations than metal salts; it does not
leave residual metals that can cause secondary contamination problems; the low concentrations of polymers reduce

Table 3
Examples of efuents treated by coagulation/occulation using chitosan.
Efuent

Reference(s)

Food, seafood and sh processing wastes

Wastewater from milk processing plant
Brewery wastewater
Surimi wash water
Inorganic suspensions (bentonite, kaolinite)
Bacterial suspensions
Efuents containing humic substances
Efuents containing dyes
Pulp and paper mill wastewater
Olive oil wastewater
Oil-in-water emulsions
Aquaculture wastewater
Efuent containing metal ions
Efuent containing phenol derivatives
Partially puried sewage
Brackish water
Raw drinking water

[6368]
[69]
[70]
[71,72]
[7378]
[7981]
[82,83]
[84,85]
[8690]
[9193]
[94]
[95]
[9698]
[99]
[100]
[101]
[102]

1341

the volume of sludge produced compared to the sludge obtained with alum for example; chitosan considerably increases the density of the sludge and facilitates its drying
compared to the sludge produced with metal salts; in addition, as biopolymers are biodegradable the sludge can be
efciently degraded by micro-organisms; two studies reported that the sludge produced from the treatment of
milk processing plant wastewater [69] and kaolinite suspensions [77] was non-toxic and could be used to stimulate growth in plants; chitosan does not add much to the
salinity of the treated water and is useable at alkaline pH.
In the coagulation/occulation process, the settling
speed of the ocs formed is also important since it inuences the overall cost and efciency [17]. It is known that
the addition of occulant has a signicant effect on the settling time when alum and/or PAC are used as coagulants. In
the case of chitosan, the increase of oc size favours the
oc settling speed and therefore reduces the settling time.
There are, of course, disadvantages which must be balanced against the benets: chitosan is only efcient over a
limited pH range and when present in excess, has a negative effect on performance (overdosing can restabilize a
dispersion and affect other process aspects); the coagulation/occulation properties depend on the different
sources of chitin/chitosan (the quality of commercial chitin
available is not uniform); another important criterion to be
taken into account concerns the variability and heterogeneity of the biopolymer chitosan: changes in the specications of the macromolecule may change coagulation
properties; each chitosan must be characterized in terms
of fraction of deacetylation, polymer weight and crystallinity because these parameters signicantly inuence its
physico-chemical properties (solubility, viscosity); there
is a need for a better standardization of the production process to be able to prepare biopolymers having the same
characteristics. These problems can rebut industrial users
[55].
The main parameter which must be taken into account
for the design of the experimental mode is solubility. However, the solubility is a very difcult parameter to control
[45]. Chitosan is a linear hydrophilic copolymer with a rigid structure containing both glucosamine and acetylglucosamine units. It is insoluble in either water or organic
solvents. However, in dilute organic acids such as acetic
acid and formic acid and inorganic acids (with the remarkable exception of sulphuric acid), the free amino groups are
protonated and the biopolymer becomes fully soluble. The
pKa of the amino group of glucosamine residues is about
6.3 and, at acidic pH (below pH 5), chitosan becomes a
soluble cationic polymer with high charge density
[44,45]. So, treatment of chitosan with acids produces protonated amine groups along the chain and this facilitates
electrostatic interactions between polymer chains and
the negatively charged contaminants (metal anions, dyes,
organic compounds, etc.). However, its solubility depends
on several parameters such as the DD and MW of the polymer, the distribution of acetyl groups along the macromolecular chain, the type and concentration of the acid used
for dissolving the polymer, the polymer concentration,
and the ionic strength. It is important to note that the DD
affects the apparent pKa and thus charge, viscosity and

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F. Renault et al. / European Polymer Journal 45 (2009) 13371348

solubility. Other important parameters for the design of

coagulation/occulation procedures using chitosan are related to the intrinsic physical and chemical characteristics
of the macromolecule (i.e., crystallinity, purity, hydrophilicity, charge density). All these characteristics may affect the
performance of chitosan. Several examples are given in part
5 concerning the impact of chitosans characteristics.
4. Mechanisms of coagulation/occulation
As already mentioned, aluminium and iron salts are
widely used as coagulants in water and wastewater treatment for removing a broad range of impurities from efuent, including colloidal particles and dissolved organic
substances. Their mode of action is generally explained in
terms of two distinct mechanisms: charge neutralization
in negatively charged colloids by cationic hydrolysis products and incorporation of impurities in an amorphous
hydroxide precipitate (sweep occulation). The relative
importance of these mechanisms depends on pH and coagulant dose. Aluminium and iron salts give cationic hydrolysis products that are strongly adsorbed on negative
particles and can give effective destabilisation. The principles governing the action of hydrolysing coagulants are
well understood [11,17,103106]. For simple metal salts
at low dosages, it is well established that charge neutralization can be an effective means of destabilising colloidal
particles. At higher coagulant dosages bulk precipitation
of metal oxide hydroxide occurs. Pre-hydrolysed coagulants are often more effective than simple metal salts
[11,15,17]. The improved performance of these materials
is probably due to the different nature of the precipitate
formed, although more detailed studies are needed [29].
Polymeric additives can also be used to cause aggregation
of particles and may act either by polymer bridging or
charge neutralization (electrostatic patch effects). The action of hydrolysing metal coagulants can involve similar
mechanisms. Readers interested in a detailed discussion
of coagulation by hydrolysing metal salts and the mechanisms involved should refer to the comprehensive reviews
of Duan and Gregory [105], and Bratby [17].
Several mechanisms such as polymer bridging, polymer
adsorption and charge neutralization (including electrostatic patch effects), depletion occulation, displacement
occulation, etc. have been proposed to explain the destabilisation of colloids and suspensions by polymers
[11,16,17,35]. Patch occulation occurs when macromolecules with a high charge density adsorb to particles and locally form positively and negatively charged areas on the
particle surface (this results in strong electrical attraction
between particles). Polymer bridging occurs when longchain polymers adsorb onto the surface of more than on
particle, thereby forming strong aggregates of large ocs.
For the case where the polymer and the adsorption site
are of opposite signs, it is postulated that charge neutralization is the major mechanism. Mechanisms of coagulation/occulation involved in the removal of dissolved and
particulate contaminants using chitosan often cited are
charge neutralization, adsorption (related to protonated
amine groups), precipitative coagulation, bridge formation

(related to the high molecular weight of biomacromolecules) and electrostatic patch. The mechanism is the following: coagulation by charge neutralization destabilizes
colloidal impurities and transfers small particles into large
aggregates (bridge formation) and adsorbs dissolved organic substances onto the aggregates by an adsorption
mechanism which can then be removed easily by ltration
and sedimentation. For example, cationic chitosan derivatives can be easily adsorbed onto the colloid surface of anionic inorganic (bentonite) suspensions due to electrostatic
attraction. Adsorbed macromolecules tend to form loops
and extend some distance from the particle surface into
the aqueous phase. Their ends also dangle and get adsorbed
by another particle forming a bridge between particles. For
effective bridging occur, the length of the biopolymer
chains should be sufcient to extend from one particle surface to another. Hence a polymer with longer chains should
be more effective than one with shorter chains. Here, occulation is interpreted as being a result of charge neutralization, patch occulation, and/or polymer bridging. The
chitosan characteristics that are important for occulation
are therefore charge density (related to its DD), molecular
weight (MW) and molecular structure. Literature data
show that the type of mechanism also depends on different
factors such as pH, ionic strength of the solution, and coagulant concentration. For example, the main mechanism for
dye coagulation with chitosan appears to be charge neutralization at acidic pH [85] and increasing chitosan dosage
increases dye removal up to a concentration resulting in
complete neutralization of anionic charges. Above that concentration, the excess of cationic charges leads to suspension re-stabilization. Numerous works claim that chitosan
is involved in a dual mechanism including coagulation by
charge neutralization and occulation by bridging mechanisms [57,85]. It should be also noted that one of the greatest differences between metal salts and cationic polymers
concerns their hydrolysis. Aluminium sulphate hydrolyses
immediately on contact with water giving rapid adsorption
reactions while chitosan is not hydrolysed [17]. A mechanism of action of polymeric occulating agents was described in detail by OMelia [106].
5. Chitosan for coagulation and occulation a review
Different reviews of chitosan-based materials have appeared concerning separation and complexation, including
membrane ltration [50] and adsorption [5356,59]. Obviously, chitosan has also been investigated as a coagulant
for the capture of contaminants from aqueous solutions
in numerous articles [57,107]. However, the studies mainly
focused on the recovery of suspended solids (SS) and colloids; in the case of dissolved contaminants there are many
fewer studies [84].
In 19751978, extensive studies by Bough and coworkers [63,64,108115] demonstrated the effectiveness
of chitosan for coagulation and recovery of SS in processing
wastes from a variety of food processing industries including poultry, eggs, cheese, meat, fruit cakes, seafood and
vegetables. These studies indicated that chitosan can reduce the SS of such processing waste by as much as 65%

F. Renault et al. / European Polymer Journal 45 (2009) 13371348

to 99% and good results were also obtained for the reduction of turbidity (TB) and chemical oxygen demand
(COD). In some instances, chitosan can be used as a coagulant aid in conjunction with a synthetic polyelectrolyte or
an inorganic salt to increase treatment performance. A
mechanism of action of chitosan as occulating agent
was described by which the polymer destabilizes the colloidal suspension by adsorption of particles with subsequent formation of particlepolymerparticle bridges.
The effectiveness of chitosan as coagulant has also been
reported by Johnson and Gallanger [116], Senstad and
Almas [117], Moore et al. [118], No et al. [57,65,119], and
Sievers et al. [120]. These authors clearly demonstrated
that chitosan has an intrinsic capacity to be used as a coagulant to reduce SS, TB and COD. These works also reported
that positively charged cationic macromolecules can destabilize the negative colloidal suspension by charge neutralization as well as by bridge formation. In addition, another
important advantage must be cited: after being used the
sludge may be disposed of with a lower environmental
impact than common metal- and synthetic polymer-based
systems [69,70,77,122]. Chi and Cheng [69] reported that
the sludge from one coagulation process could be used directly as a feed supplement. Divakaran and Pillai [77] suggested that the sludge produced during the occulation of
kaolinite suspensions could be safely disposed off in landlls. However, such re-use needs to be carefully assessed
and its harmlessness must be checked.
There is recent literature concerning the evaluation of
the coagulation/occulation performance of chitosan. This
biopolymer has an extremely high afnity for many classes
of contaminants: it has demonstrated outstanding removal
properties for natural organic matter [123], humic substances [82,124,125], inorganic suspensions [74,75], dye
molecules [84,85], metal cations [97,98], proteins [70],
phenolic and aromatic derivatives [99], oil and grease
[9194], bacterial [81,126] and algal [127] suspensions.
For humic materials, Guibal et al. [84] showed that chitosan can be used as a primary coagulant or as a occulant
after coagulation: it has characteristics of both coagulants
and occulants. Ahmad et al. [91] demonstrated it was a
very effective coagulant to remove the residual oil content
from palm oil mill efuent compared to alum and PAC.
Divakaran and Pillai [127] showed that chitosan reduced
algal contents effectively by occulation and settling. However, they noted that the occulation was very sensitive to
pH. Chitosan can be used not only as a coagulant and/or
occulant but also as a bactericide. For example, Chung
[95] showed that this biopolymer was useful not only for
the removal of SS, organic and inorganic compounds, TB,
and COD, but also for the removal of pathogens. Huang
and co-workers [121,122] showed that chitosan could be
a promising substitute for alum and PAC in the coagulation
of colloidal particles because of its suitability for coagulation without posing any health threats as residual aluminium and other synthetic polymers do. To reach the same
level of turbidity removal, the required amount of chitosan
is only half that of PAC. Chitosan coagulants also produced
larger ocs of better quality and faster settling velocity
[122]. They also indicated that replacing PAC with chitosan
in the water treatment process can be cost effective.

1343

Coagulation/occulation processes have been widely

used as pre-treatments to remove suspended particles
and colouring materials in primary treatment prior to biological treatment. However, dye molecules, in particular
reactive dyes [89], cannot be easily removed by conventional coagulants. Guibals group [7375,84,85,128130]
published a series of papers on the ability of chitosan to
act as an effective coagulant to treat not only particulate
suspensions but also dissolved substances. In particular,
they showed that colour can be removed either by adsorption onto solid-state chitosan or by coagulation/occulation using dissolved-state chitosan. The reactivity of
amine groups was signicantly increased when dissolved
biopolymer was used [84]. The authors explained their results by the fact that using chitosan in the dissolved state
improves the accessibility and availability of reactive sites
compared to the solid state [85]. Comparison of saturation
values for adsorption and coagulation/occulation proved
that the molar ratio between the amine groups of the biopolymer and the sulfonic groups of the dye molecules was
much greater when using chitosan in the dissolved state
(coagulation/occulation) than in the solid state (adsorption). The conformation of polymer chains also seems to
be the key parameter in the comparison of removal performance [84]. All these works showed that the coagulation/
occulation process involved several mechanisms such as
charge neutralization, precipitative coagulation, bridging,
electrostatic patch and aggregation phenomenon. In general, a charge neutralization associated to bridging effect
is sufcient to explain the results [130]. However, the type
of mechanism depends mainly on coagulant dosage and
pH. They observed that an excess of cationic charge contributes to re-stabilising the suspension and reducing the
efciency of the process. The authors also noted that the
optimum dosage correlated well with the initial concentration of the pollutant indicating that the addition of the biopolymer could be easily monitored by determining the
pollutant concentration in the solution. The effect of pH
can be attributed to differences in the protonation of the
biopolymer amine groups, changes in the conformation
of the macromolecule chain (chain repulsion) and the
structure of the ocs. In neutral solutions, because of the
more coiled structure, the biopolymer is able to produce
larger and denser ocs. In acidic solutions, chitosan becomes a more extended chain (more charged) and therefore produces smaller, looser ocs, conrming the
previous results reported by Huang et al. [121]. These
authors showed that when the positive charge of chitosan
is neutralised by the negative ion in acid solution, the conformation of the biopolymer changes. Huang et al. [121]
also indicated that the chitosan becomes more compact
in more acidic solution and therefore lowers the viscosity
of the solution. The length of polymer chains (related to
the MW of the biopolymer) is also an important parameter
to be considered for optimising the use of chitosan in coagulation/occulation. However, the results and their interpretation also depend on the type of contaminant. Guibal
et al. [84] showed that the MW of chitosan did not affect
the coagulation/occulation of humic acid (HA). They assumed that the more complex and exible structure of
HA may limit the inuence of MW. In the case of bentonite

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F. Renault et al. / European Polymer Journal 45 (2009) 13371348

suspensions, they noted that the performance decreased

with decreasing MW while for kaolinite suspensions the
impact of MW was not very marked. Increasing the biopolymer concentration reduced the impact of MW. Guibal
and co-workers [73,84,128] concluded that chitosan offers
a promising alternative to the use of mineral reagents
(alum or ferric salts) or synthetic polymers as coagulants
or coagulant aids.
Other studies of dye-chitosan interactions have been
carried out. Sanghi and Bhattacharya [89] showed that
chitosan, as coagulant aid, is very effective for decolouring
acidic and direct dyes. They also reported that reactive dyes
with anthraquinone groups were the most difcult to decolour. Gandjidoust et al. [90] reported that the natural coagulant chitosan resulted in the highest removal in both colour
and TOC as compared to synthetic polymers (poly(acrylmide) or PAM, poly(ethyleneimine) or PEI) and a chemical
coagulant (alum). Similar conclusions were reported by
Rodrigues et al. [86] and Wang et al. [87] for the treatment
of paper pulp and paper mill wastewater. Our group has also
proposed modied chitosan-based biopolymers as adsorbents and/or coagulants for the removal of SS; DCO and colour from pulp and paper mill efuent [53,136138] (Fig. 1).
Overall, these studies report that the binding mechanism of
dyes by polymers can be described as adsorption, hydrogen
bonding, hydrophobic or electrostatic interaction.
The data from the literature show that the control of the
performance of chitosan in coagulation/occulation process depends on the following factors:
(i) the origin and the nature of the chitosan (i.e., its
intrinsic characteristics such as DD and MW, and
the activation conditions of the raw biopolymer);
(ii) the inuence of process variables such as the equipment installed, the addition of reagents, the dosage

of the coagulant, the type of acid used to dissolve

the chitosan, the reaction time, the rate of rotation
and the speed gradient;
(iii) the chemistry of the pollutants (type of pollutants
and their physico-chemical properties such as polarity and hydrophobicity);
(iv) and nally the solution conditions referring to its
pH, the ionic strength, the zeta potential, the colour,
the concentration of the colloidal particles, the presence of impurities (i.e., dissolved salts or trace elements such as ions and chemicals) and temperature.
It is generally expected, and often found, that the coagulationocculation efciency of chitosan is proportional
to its charge and consequently highly N-deacetylated samples are usually applied as coagulant and occulant materials. However, it is important to note that several
contradictory observations have been reported and the
reader is encouraged to refer to the original papers for
complete information on experimental conditions in the
coagulation studies used.
Chitosan can dissolve in carboxylic acid solutions or in
inorganic solutions. Acetic acid is a common solvent for
this biomacromolecule. However, Huang et al. [121] reported that this organic solvent increased the organic content of suspensions. They suggested using hydrochloric
acid as an alternative solvent. In addition, they also indicated that it was important to search for the optimal acid
concentrations since the viscosity of dissolved chitosan
coagulants decreases with increasing concentrations of
acid. In another work [122], the authors conrmed that
the performances of chitosan depend on the process variables such as the dosage of chitosan, the speed of mixing
and pH. The optimum chitosan dosage was smaller in
acidic solutions, although smaller ocs were produced,

Fig. 1. Photograph of samples analysed (a) efuent after PAC treatment; (b) raw efuent; (c) efuent after chitosan-based material treatment (experiments
were performed using a Jar-Test equipment; DCO and turbidity values were obtained after a 2-min settling time).

F. Renault et al. / European Polymer Journal 45 (2009) 13371348

and increasing the speed during rapid mixing can also reduce the optimum dosage. The authors supposed that
destabilization of particles was enhanced by the increase
in charged groups (in acidic solutions, there is an increase
in the number of protonated amine groups on chitosan)
followed by charge neutralization, resulting in a decrease
in optimum dosage. The authors also found a linear relationship between the DD and the optimal chitosan dosage,
which indicates that amino groups of macromolecules are
the active site for coagulation [121]. There is a relationship
between the DD and the treatment time. The speed of mixing may affect the coagulation only before the optimal dosage is reached. Huang and co-workers [121,122] concluded
that the optimal pre-treatment condition to prepare chitosan coagulant and its dosage were the key parameters to
evaluate the coagulation performance.
Guibal et al. [84,129] showed the characteristics of
chitosan (mainly DD and MW) slightly affected the coagulationocculation performance. The DD had more effect
on bentonite suspensions and dye solutions than on kaolin
and humic acid suspensions. Very low doses of biopolymer
were required for the treatment of concentrated suspensions of bentonite; sedimentation was fast and very low
turbidity was obtained within a few minutes settling time;
the doses were signicantly lower when the pH of the suspension was less than the intrinsic pKa of chitosan. In contrast to the ndings of Guibal and co-workers, Chung [95],
studying the removal of SS, COD, TB and organic compounds from aquaculture wastewater by chitosan, observed that the treatment efciency of chitosan was
highly dependent on its DD and on the pH of the solution.
A high DD and low pH value improved the performance of
the coagulation process. Huang et al. [121] also showed
that the charge density of chitosan, and its coagulation performance, was directly proportional to the DD.
Wibowo et al. [71] studied the inuence of the MW and
DD of chitosan on the removal efciency of proteins. They
concluded that the difference in MW and DD values between samples could not explain the signicant differences
in protein recovery. No meaningful correlation was apparent. Kvinnesland and degaard [124], studying the effects
of polymer characteristics on separation in humic substance removal by cationic polymer coagulation, showed
that polyelectrolyte MW did not show any signicant effect on the coagulation of humic substances. Chen et al.
[135] reported that the DD of chitosan had limited effect
on the occulation performance while its MW played a
key role. The higher the MW, the better the occulation.
Large differences were found by Strand et al. [80,81,126]
in the efciency of chitosan materials to occulate bacterial suspensions, both regarding the effective biopolymer
concentrations and the type of chitosan giving the best
performance. In particular, the effect of MW on occulation performance was found to be of importance. The
choice of the optimal chitosan type for a given application
is a tricky task [126].
The interaction between chitosan and mineral colloids
(bentonite) has been investigated by Roussy et al. [75].
They showed that it was not necessary to add large
amounts of chitosan: doses as low as 0.20.5 mg/L were
sufcient to achieve the complete coagulationocculation

1345

of the solutions in a very short time (a few minutes were

sufcient). With optimised selection of polymer characteristics, the required dosage can be decreased to 0.1 mg/L or
below depending on the biopolymer. Their investigations
clearly indicated that chitosan had a natural selectivity
for mineral colloids. However, they reported that the DD
of chitosan inuences the coagulation and its MW the occulation mechanism. Similar conclusions were reported by
Huang and Chen [76] for the removal of bentonite. They
indicated that the coagulation behaviour of chitosan with
respect to kaolinite was different from that with bentonite.
Chitosan failed to form a good aggregate with kaolinite.
However, in contrast to this, Divakaran and Pillai [77] concluded that chitosan was a useful occulant for kaolinite
suspensions in water.
Ahmad et al. [91], studying the removal of residual oil in
palm oil mill efuent by chitosan, showed that chitosan requires lower dosages to destabilize the oil residue mainly
by charge neutralization mechanisms, while the dosages
needed for alum and PAC were 10 times more than for
chitosan. Chitosan also reacts faster to residual oil compared to inorganic coagulants: the ocs produced by chitosan appear rapidly and grow fast to form larger ocs which
sediment easily. The mechanism are different: for chitosan,
the authors suggest that the biopolymer agglomerates the
residual oil suspended in the efuent (by a charge neutralization mechanism) and adsorbs it by an adsorption mechanism, while alum and PAC just agglomerate and bridge
the residual oil (they do not adsorb it). In another work,
Ahmad et al. [92] conrmed that chitosan derivatives possess a number of functional groups responsible for the
binding of pollutants either by chemical and/or physical
adsorption. The results can be mainly explained on the basis of the higher charge density of chitosan requiring lower
doses to destabilize the solution. The charge mechanism
was also introduced by Huang and Chen [76] and Pan
et al. [122] in the removal of colloidal particles by chitosan,
and Bolto et al [123] and Szygula et al. [130] in the removal
of natural organic matter and dyes. Different conclusions
have been reported by Strand et al. [81], and Meyssami
and Kasaeian [93]. Strand et al. [81], applying chitosan to
occulate bacterial suspensions, pointed out the predominant role of bridging in the occulation mechanism.
Meyssami and Kasaeian [93], studying the treatment of
an olive oil water suspension by chitosan, noted that the
presence of sodium chloride in the solution aids the coagulation phenomenon and they concluded that the major
mechanism is chemical bridging rather than charge neutralization. Wu et al. [98] investigated the use of chitosan
as occulant for coprecipitation of Mn(II) and removal of
SS, and reported that charge neutralization, occulation
and adsorption occur simultaneously.
Several workers have suggested that although chitosan
as such is very useful as a coagulant, it may be advantageous to chemically modify the biopolymer, e.g., by grafting
reactions. These modications can improve the removal
performance of the chitosan as patented by Laue and Hunkeler [42] and also reported by Wang et al. [131], Mishra
et al. [132], Wang et al. [133], Chavasit and Antonio Torres
[134], and Crini et al. [136]. For example, Mishra et al. [132]
reported that chitosan-g-N-vinyl formamide showed better

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F. Renault et al. / European Polymer Journal 45 (2009) 13371348

results for metal ion adsorption and occulation than chitosan. The grafted copolymers generally possess the main
properties of both initial components, and they are chemically stable and usually biodegradable [131].
6. Conclusions
Chitosan possesses several intrinsic properties such as
its non-toxicity, its biodegradability and its outstanding
chelation behaviour that make it an effective coagulant
and/or occulant for the removal of contaminants in the
dissolved state. It has the physico-chemical characteristics
of both coagulants and occulants, i.e., high cationic charge
density and long polymer chains, leading to bridging of
aggregates and precipitation. Numerous works have demonstrated that chitosan and its derivatives (in particular
grafted biopolymers) can be a potential substitute for
metallic salts and synthetic polyelectrolytes in the treatment of wastewater for the removal of both particulate
and dissolved substances. However, more studies are required to rene the optimisation of the properties of chitosan such as the degree of deacetylation which can
inuence coagulation and the molecular weight which
affects occulation.
Acknowledgements
Authors thank OSEO ANVAR (Besanon, France) and
INRA Transfert (Dpartement Valorisation, Paris, France)
for nancial support (Programme Chitodex Project Development of biocoagulants). The research grants given by
the French Ministry of Research and Education, the CNRS
and the Rgion of Franche-Comt which provide nancial
support for the Ph.D. students F. Renault and B. Sancey
are gratefully acknowledged. Thanks are due to the three
groups involved in our research program on pollutant complexation by chitosan-based materials: that of Dr. Giangiacomo Torri from G. Ronzoni Institute (Milan, Italy), of Prof.
Bernard Martel from University of Lille (France) and of
Prof. Yayha Lekchiri from University of Oujda (Morocco).
We acknowledge the constant contribution of Dr. Nadia
Morin-Crini (Chrono-environment Laboratory, Besanon,
France) to this research program. The authors also thank
Dr. Peter Winterton (University of Toulouse, France) for
its critical reading of this review, G. Ronzoni Institute
(Milan, Italy) for providing of chitosan samples, and Mr.
Jean-Claude Jeune (ARIST, Besanon, France) for providing
of patents.
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