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vora, Portugal
a r t i c l e i n f o
Article history:
Received 23 June 2008
Received in revised form
8 November 2008
Accepted 24 November 2008
Available online 4 March 2009
Keywords:
Adsorbents
Adsorption
Dye removal
Dyes
Low-cost adsorbents
Non-conventional adsorbents
Wastewater treatment
a b s t r a c t
Dyes are an important class of pollutants, and can even be identied by the human eye. Disposal of dyes
in precious water resources must be avoided, however, and for that various treatment technologies are in
use. Among various methods adsorption occupies a prominent place in dye removal. The growing
demand for efcient and low-cost treatment methods and the importance of adsorption has given rise to
low-cost alternative adsorbents (LCAs). This review highlights and provides an overview of these LCAs
comprising natural, industrial as well as synthetic materials/wastes and their application for dyes
removal. In addition, various other methods used for dye removal from water and wastewater are also
complied in brief. From a comprehensive literature review, it was found that some LCAs, in addition to
having wide availability, have fast kinetics and appreciable adsorption capacities too. Advantages and
disadvantages of adsorbents, favourable conditions for particular adsorbateadsorbent systems, and
adsorption capacities of various low-cost adsorbents and commercial activated carbons as available in
the literature are presented. Conclusions have been drawn from the literature reviewed, and suggestions
for future research are proposed.
2008 Elsevier Ltd. All rights reserved.
1. Introduction
Saving water to save the planet and to make the future of
mankind safe is what we need now. With the growth of mankind,
society, science, technology our world is reaching to new high
horizons but the cost which we are paying or will pay in near future
is surely going to be too high. Among the consequences of this rapid
growth is environmental disorder with a big pollution problem.
Besides other needs the demand for water (Water for People
Water for Life United Nations World Water Development Report
UNESCO) has increased tremendously with agricultural, industrial
and domestic sectors consuming 70, 22 and 8% of the available
fresh water, respectively and this has resulted in the generation of
large amounts of wastewater (Helmer and Hespanhol, 1997; Lehr
et al., 1980; Nemerrow, 1978) containing a number of pollutants.
One of the important class of the pollutants is dyes, and once they
enter the water it is no longer good and sometimes difcult to treat
as the dyes have a synthetic origin and a complex molecular
structure which makes them more stable and difcult to be bio-
degraded (Forgacs et al., 2004; Rai et al., 2005).
Mankind has used dyes for thousands of years (Christie, 2007)
and the earliest known use of a colourant is believed to be by
Neanderthal man about 1,80,000 years ago. However, the rst
known use of an organic colourant was much later, being nearly
4000 years ago, when the blue dye indigo was found in the
wrappings of mummies in Egyptian tombs (Gordon and Gregory,
1983). Till the late nineteenth century, all the dyes/colourants were
more or less natural with main sources like plants, insects and
mollusks, and were generally prepared on small scale. It was only
after 1856 that with Perkins historic discovery (Hunger, 2003;
Venkataraman, 1965) of the rst synthetic dye, mauveine, that dyes
were manufactured synthetically and on a large scale.
Dye molecules comprise of two key components: the chromo-
phores, responsible for producing the colour, and the auxochromes,
which can not only supplement the chromophore but also render
the molecule soluble in water and give enhanced afnity (to attach)
toward the bers. Dyes exhibit considerable structural diversity
and are classied in several ways. These can be classied (Hunger,
2003) both by their chemical structure and their application to the
ber type. Dyes may also be classied on the basis of their solu-
bility: soluble dyes which include acid, mordant, metal complex,
direct, basic and reactive dyes; and insoluble dyes including azoic,
sulfur, vat and disperse dyes. Besides this, either a major azo linkage
or an anthraquinone unit also characterizes dyes chemically. It is
worthwhile noting that the azo dyes are the one most widely used
and accounts 6570% of the total dyes produced. Though, the
classication of dyes on basis of structure is an appropriate system
* Corresponding author. Tel.: 91 1332 285801; fax: 91 1332 273560.
E-mail address: vinodfcy@iitr.ernet.in (V.K. Gupta).
Contents lists available at ScienceDirect
Journal of Environmental Management
j ournal homepage: www. el sevi er. com/ l ocat e/ j envman
0301-4797/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2008.11.017
Journal of Environmental Management 90 (2009) 23132342
and has many advantages, like it readily identies dyes as
belonging to a group and having characteristic properties, e.g., azo
dyes (strong, good all-round properties, cost-effective) and
anthraquinone dyes (weak, expensive), there are a manageable
number of chemical groups (about a dozen). Besides these, both the
synthetic dye chemist and the dye technologist use this classica-
tion most widely. However, the classication based on application
is advantageous before considering chemical structures in detail
because of the complexities of the dye nomenclature fromthis type
of system. It is also worth to point that classication by application
is the principal system adopted by the Colour Index (C.I.). In the
present review we will try to use the dye names based on their
application or their C.I. name/number. This system includes the
name of the dye class, its hue, and a number. A ve digit C.I. number
is assigned to a dye when its chemical structure has been disclosed
by the manufacturer. It is also worth to note here that though a dye
has a C.I. number, the purity and precise chemical constitution may
vary depending upon the name. An example of dye acid blue 92 is
given in Fig. 1 (Sabnis, 2008).
Some properties of dyes classied on their usage (Christie, 2007;
Hunger, 2003) are discussed in brief here.
Acid Dyes: used for nylon, wool, silk, modied acrylics, and also
to some extent for paper, leather, ink-jet printing, food, and
cosmetics. They are generally water soluble. The principal chemical
classes of these dyes are azo (including premetallized), anthraqui-
none, triphenylmethane, azine, xanthene, nitro and nitroso.
Cationic (Basic) Dyes: used for paper, polyacrylonitrile, modied
nylons, modied polyesters, cation dyeable polyethylene tere-
phthalate and to some extent in medicine too. Originally they were
used for silk, wool, and tannin-mordanted cotton. These water-
soluble dyes yield coloured cations in solution and thats why are
called as cationic dyes. The principal chemical classes are dia-
zahemicyanine, triarylmethane, cyanine, hemicyanine, thiazine,
oxazine and acridine.
Disperse Dyes: used mainly on polyester and to some extent on
nylon, cellulose, cellulose acetate, and acrylic bers. These are
substantially water-insoluble nonionic dyes used for hydrophobic
bers from aqueous dispersion. They generally contain azo,
anthraquinone, styryl, nitro, and benzodifuranone groups.
Direct Dyes: used in the dyeing of cotton and rayon, paper,
leather, and, to some extent to nylon. They are water-soluble
anionic dyes, and, when dyed from aqueous solution in the pres-
ence of electrolytes have high afnity for cellulosic bers. Generally
the dyes in this class are polyazo compounds, along with some
stilbenes, phthalocyanines and oxazines.
Reactive Dyes: generally used for cotton and other cellulosics,
but are also used to a small extent on wool and nylon. These dyes
form a covalent bond with the ber and contain chromophoric
groups such as azo, anthraquinone, triarylmethane, phthalocya-
nine, formazan, oxazine, etc. Their chemical structures are simpler,
absorption spectra show narrower absorption bands, and the
dyeings are brighter making them advantageous over direct dyes.
Solvent Dyes: used for plastics, gasoline, lubricants, oils, and
waxes. These dyes are solvent soluble (water insoluble) and generally
nonpolar or little polar, i.e., lacking polar solubilizing groups such as
sulfonic acid, carboxylic acid, or quaternary ammonium. The prin-
cipal chemical classes are predominantly azo and anthraquinone, but
phthalocyanine and triarylmethane are also used.
Sulfur Dyes: used for cotton and rayon and have limited use with
polyamide bers, silk, leather, paper, and wood. They have inter-
mediate structures and though they forma relatively small group of
dyes the lowcost and good wash fastness properties make this class
important from an economic point of view.
Vat Dyes: used for cotton mainly to cellulosic bers as soluble
leuco salts and for rayon and wool too. These water-insoluble dyes
are with principal chemical class containing anthraquinone
(including polycyclic quinones) and indigoids.
Besides these, there are some other classes too like azoic having
azo groups used for cotton and other cellulosic materials; uorescent
brighteners having stilbene, pyrazoles, coumarinandnaphthalimides
used for soaps and detergents, bers, oils, paints, and plastics and
mordant having azo and anthraquinone used for wool, leather,
natural bers after pretreating with metals and anodized aluminium.
Overall at present there are more than 100,000 commercial dyes
with a rough estimated production of 7 10
5
110
6
tons per year
(Christie, 2007; Hunger, 2003; Husain, 2006; Meyer, 1981; Zollinger,
1987). Of such a huge production the exact data on the quantity of
dyes discharged in environment is not available. However, it is
reported that 1015% of the used dyes enter the environment
through wastes (Hai et al., 2007; Husain, 2006). The big consumers of
dyes are textile, dyeing, paper and pulp, tannery and paint industries,
and hence the efuents of these industries as well as those from
plants manufacturing dyes tend to contain dyes in sufcient quan-
tities. Dyes are considered an objectionable type of pollutant because
they are toxic (Bae and Freeman, 2007; Christie, 2007; Combes and
Havelandsmith, 1982; Nemerow and Doby, 1958) generally due to
oral ingestion and inhalation, skin and eye irritation, and skin
sensitization leading to problems like skin irritation and skin sensi-
tization and also due to carcinogenicity (Christie, 2007; Hatch and
Maibach, 1999; Rai et al., 2005). They impart colour to water which is
visible to human eye and therefore, highly objectionable on aesthetic
grounds. Not only this, they also interfere with the transmission of
light and upset the biological metabolism processes which cause the
destruction of aquatic communities present inecosystem(Kuo, 1992;
Fig. 1. Acid blue 92 (Sabnis, 2008). C.I. Name: C.I. Acid Blue 92. C.I. Number: C.I. 13390.
Other names: Acid Blue 92; Acid Blue A; Acid Fast Blue R; Acid Leather Blue R; Acid
Wool Blue RL; Acilan Fast Navy Blue R; Airedale Blue RL; Amacid Fast Blue R; Anazo-
lene sodium; Benzyl Blue R; Benzyl Fast Blue R; Best Acid Blue 3R; Bucacid Fast Wool
Blue R; Coomassie Blue RL. CA Index Name: 2,7-Naphthalenedisulfonic acid, 4-
hydroxy-5-[[4-(phenylamino) 5-sulfo-1- naphthalenyl]azo]-, trisodium salt. CAS
Registry Number: 3861-73-2. Chemical/Dye Class: Azo. Molecular Formula:
C
26
H
16
N
3
O
10
S
3
Na
3.
Molecular Weight: 695.59. Physical Form: Dark bluish-black
powder. Solubility: Soluble in water, acetone; slightly soluble in ethanol, glycerol. UV-
Visible (l
max
): 571 nm, 585 nm, 580590 nm.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2314
Walsh et al., 1980). Further, the dyes have a tendency to sequester
metal and may cause microtoxicity to sh and other organisms
(Walsh et al., 1980). As such it is important to treat coloured efuents
for the removal of dyes.
For this various methodologies have been presented and even
reviewed too (Aksu, 2005; Banat et al., 1996; Crini, 2006; Crini and
Badot, 2008; Delee et al., 1998; dos Santos et al., 2007; Forgacs et al.,
2004; Fu and Viraraghavan, 2001a; Hai et al., 2007; Kandelbauer
and Guebitz, 2005; McMullan et al., 2001; Ozyurt and Atacag, 2003;
Pearce et al., 2003; Rai et al., 2005; Robinson et al., 2001; Sanghi
and Bhattacharya, 2002; Slokar and Majcen Le Marechal, 1998;
Stolz, 2001; van der Zee and Villaverde, 2005; Vandevivere et al.,
1998; Wesenberg et al., 2003; Wojnarovits and Takacs, 2008). Some
of these are discussed in the subsequent paragraphs.
2. Methods of dye removal
Few decades earlier, the dyes selection, application and use were
not given a major consideration with respect to their environmental
impact. Even the chemical composition of half of the dyes used in the
industry was estimatedtobe unknown. Withthegrowingconcernon
health mainly onaesthetic grounds, it was more from80s that people
started paying much attention to the dye wastes too. In the last few
years, however, more information on the environmental conse-
quences of dyestuff usage has become available and the dye manu-
facturers, users and government themselves are taking substantial
measures to treat the dye containing wastewaters. Since initially
there was no discharge limit the treatment of dye wastewater started
just with some physical treatments such as sedimentation and
equalisation to maintain the pH, total dissolved solids (TDS) and total
suspended solids (TSS) of the discharged water. Later secondary
treatments such as the use of lter beds for biodegradation and, more
recently, the introduction of the activated sludge process (aerobic
biodegradation) were used to treat the dye wastewater. Normally
industrial-wastewater treatment processes (Perryet al., 1997) consist
of following steps like: Pretreatment industrial-wastewater
streams prior to discharge to municipal sewerage systems or even to
a central industrial sewerage system are pretreated doing equal-
isation, neutralization; then they undergo primary treatment and
wastewater is directed toward removal of pollutants with the least
effort. Suspended solids are removed by either physical or chemical
separation techniques and handled as concentrated solids; then they
are given a secondary treatment usually involving microorganisms
(biological treatment) primarily bacteria which stabilize the waste
components. The third step is physicalchemical treatment or
tertiary treatment and the processes included in this are adsorption,
ion exchange, stripping, chemical oxidation, and membrane separa-
tions. All of these are more expensive than biological treatment but
are used for the removal of pollutants that are not easily removed by
biological methods. Thoughthese are generally utilized inseries with
biological treatment, sometimes they are used as stand-alone
processes too. The nal stepbeingthe sludge processing anddisposal.
Dye wastewater are also treated in more or less a similar way,
nevertheless, there is no single standard methodology/treatment
procedure used for all types of wastes.
We are classifying the methodologies generally adopted to treat
dye wastewater in four categories: (i) physical (ii) chemical (iii)
biological and (iv) acoustical, radiation, and electrical processes.
Some of the methodologies lying in above mentioned categories
are discussed in brief in subsequent paragraphs.
Sedimentation is the basic form of primary treatment used at
most municipal and industrial-wastewater treatment facilities
(Cheremisinoff, 2002). There are a number of process options
available to enhance gravity settling of suspended particles,
including chemical occulants, sedimentation basins, and clariers.
Filtration technology is an integral component of drinking
water and wastewater treatment applications which includes
microltration, ultraltration, nanoltration, and reverse osmosis.
This has been investigated for colour removal (Avlonitis et al., 2008;
Cheremisinoff, 2002). Each membrane process is best suited for
a particular water treatment function (Cheremisinoff, 2002).
Among them, microltration is of not much use for wastewater
treatment because of its large pore size, and though ultraltration
and nanoltration (Cheremisinoff, 2002; Marmagne and Coste,
1996) techniques are effective for the removal of all classes of
dyestuffs, dye molecules cause frequent clogging of the membrane
pores making the separation systems of limited use for textile
efuent treatment. The main drawbacks are high working pres-
sures, signicant energy consumption, high cost of membrane and
a relatively short membrane life which makes their use limited for
treating dye wastewater. Reverse osmosis forces water, under
pressure, through a membrane that is impermeable to most
contaminants. The membrane is somewhat better at rejecting salts
than it is at rejecting non-ionized weak acids and bases and smaller
organic molecules generally molecular weight below 200. Reverse
osmosis (Al-Bastaki, 2004; Marcucci et al., 2001; Sostar-Turk et al.,
2005) is effective decolouring and desalting process against the
most diverse range of dye wastes, and has been successfully
employed for recycling. The water produced by reverse osmosis,
will be close to pure H
2
O.
Chemical treatment of dye wastewater with a coagulating/
occulating agent (Shi et al., 2007; Wang et al., 2006a; Zhou et al.,
2008) is one of the robust ways to remove colour. The process
involves adding agents, such as aluminum (Al
3
), calcium (Ca
2
) or
ferric (Fe
3
) ions, to the dye efuent and induces occulation.
Besides these other agents (Mishra and Bajpai, 2006; Mishra et al.,
2006; Yue et al., 2008) have also been used for the process.
Sometimes combination (Wang et al., 2007) of two may also be
added to enhance the process. Generally, the process is economi-
cally feasible (but sometimes becomes expensive due to the cost of
chemicals) with satisfactory removal of disperse, sulfur, and vat
dyes. However, the main drawback of the process is that the nal
product is a concentrated sludge produced in large quantities also,
besides this, the removal is pH dependent (Kace and Linford, 1975;
Lee et al., 2006). This process is not good for highly soluble dyes and
the result with azo, reactive, acid and especially the basic dyes (Hai
et al., 2007; Raghavacharya, 1997) are generally not good.
Oxidation is a method by which wastewater is treated by using
oxidizing agents. Generally, two forms viz. chemical oxidation and
UV assisted oxidation using chlorine, hydrogen peroxide, fentons
reagent, ozone, or potassium permanganate are used for treating
the efuents, especially those obtained from primary treatment
(sedimentation). They are among the most commonly used
methods for decolourisation processes since they require low
quantities and short reaction times. They are used to partially or
completely degrade the dyes (generally to lower molecular weight
species such as aldehydes, carboxylates, sulfates and nitrogen).
However, a complete oxidation of dye can theoretically reduce the
complex molecules to carbon dioxide and water. It is worth to note
that pH and catalysts play an important role in oxidation process.
Chlorine is a strong oxidizing agent used and may also be applied
as calcium hypochlorite and sodium hypochlorite. In addition to
being the most widely used disinfectant for water treatment, it is
extensively used for reduction of colour like pulp and textile
bleaching. Reactive, acid, direct and metal complex dyes, which are
water soluble are decolourised readily by hypochlorite, but water-
insoluble disperse andvat dyes are resistant to decolourisationinthis
process (Namboodri et al., 1994a,b). It has been reported that decol-
ourisation of reactive dyes generally require long reaction times,
while metal complex dye solution remains partially coloured even
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2315
after an extended period of treatment. Dyes (Omura, 1994) having
amino or substituted amino groups on a naphthalene ring, are most
susceptible to chlorine and decolourise more easily than other dyes.
Oxidation can be enhanced through control of pH and also by using
catalysts, e.g., in the decomposition of metal complex dyes metals,
like iron, copper, nickel andchromium, are liberatedandthese metals
have a catalytic effect that increases decolourisation. Though the use
of chlorine gas is a low-cost methodology for decolourising dye
wastewater, its use causes unavoidable side reactions, producing
organochlorine compounds including toxic trihalomethane, thereby
increasing the absorbable organic halogens content of the treated
water, also the liberation of metals in metal complex dyes may cause
corrosion in metallic vessels.
Hydrogen peroxide (H
2
O
2
) is a very pale blue liquid which
appears colourless in a dilute solution, slightly more viscous than
water. It has strong oxidizing properties and is therefore a powerful
bleaching agent that is used for bleaching paper besides other uses.
About 50% of the worlds production of hydrogen peroxide in 1994
was used for paper and pulp bleaching (Hage and Lienke, 2006).
Hydrogen peroxide is also used for making peroxidase enzymes,
which are used for decolourisation of dyes (Morita et al., 1996).
However, the process is pH dependent and produces sludge.
Fentons reagent, a solution of hydrogen peroxide and an iron
catalyst is also used to oxidize dye wastewaters (Meric et al., 2003;
Wang, 2008) and is stronger than hydrogenperoxide. Generally, it is
effective (Kim et al., 2004) in decolourization of both soluble and
insoluble dyes (acid, reactive, direct, metal complex dyes) though
some dyes like vat and disperse were found to be resistant to it, e.g.,
dyes (Gregor, 1992) like palanil blue 3RT was resistant to Fentons
reagent, dyes like remazol brilliant blue B, sirrus supra blue BBR,
indanthrene blue GCD, irgalan blue FGL and helizarinblue BGT, have
been reported to be signicantly decolourised. It is to be noted that,
not only is colour removed, but chemical oxygen demand (except
with reactive dyes), total organic carbon and toxicity are also
reduced. The process is also applicable even with high-suspended
solid concentrationandis preferredfor wastewater treatment when
a municipality allows the release of Fentons sludge into sewage.
Froma biological point of view, it is belived that not only the quality
of the sludge is improved, but the phosphates can also be elimi-
nated. The main drawbacks are that it is usually effective within
narrow pH range (Cheng et al., 2004) of <3.5, involves sludge
generation and takes longer reaction time.
Ozonation carried out by ozone generated fromoxygen has been
studied by various workers and has been found to be an very
effective way of decolourizing textile efuents (Perkins et al., 1996;
Soares et al., 2006; Wu et al., 2008b). Sundrarajan et al. (2007)
studied the ozonation for colour removal (reactive dyes) and found
that colour removal of the efuent can be achieved in 5 min of
contact time for yellow and blue shades at an ozone consumption
of 37.5 and 36 mg L
1
, respectively and suggested that ozonation is
efcient in decolourization of exhausted dye bath efuents con-
taining conventional reactive dyes. The decolourization of aqueous
C.I. reactive blue 15 was studied by Wu et al. (2008b) in a semibatch
reactor, who found the process to be a pseudo-rst-order reaction
with respect to the dye. The authors observed that ozonation also
effectively removed chemical oxygen demand (COD). However,
some authors reported that ozonation (Snider and Porter, 1974;
Sundrarajan et al., 2007) while removing colour effectively gener-
ally does not minimize COD signicantly. In a study, to know the
possibility of recycling of reactive dye bath for dyeing of cotton
fabric after decolouration Senthilkumar and Muthukumar (2007)
used ozone. Cold brand reactive dyes namely red 5MR and golden
yellow MR were used and the oxidation was carried out by ozone.
Authors suggested that ozonation can be used to remove
completely the colour and chemical oxygen demand too to an
extent, which is sufcient for water reuse even in critical conditions
as dyeing with light tones.
Electrochemical methodology (Gupta et al., 2007b; Lin and
Peng, 1994) as a tertiary treatment is also used to remove colour.
Decolourisation can be achieved either by electro oxidation with
non-soluble anodes or by electro-coagulation using consumable
materials. Several anode materials, like iron, conducting polymer
a boron doped diamond electrode etc., with different experimental
conditions, have been used successfully in the electro-degradation
of dyes (Dogan and Turkdemir, 2005; Faouzi et al., 2007; Oliveira
et al., 2007a). A colour removal (Lopes et al., 2004) of 83100% was
observed for Direct Red 80 using three different electrodes: iron,
polypyrrole doped with chromium and boron doped diamond
electrode. This technique is effective in decolourisation of soluble
and insoluble dyes with reduction of COD. It is worthwhile pointing
that among other variables the rate of colour and organic load
removal depends, on the anodes material and the working
potential. Nevertheless, the main drawbacks are high electricity
cost and sludge production and also pollution from chlorinated
organics, heavy metals due to indirect oxidation.
Advanced Oxidation Processes (AOPs) are the processes
involving simultaneous use of more than one oxidation processes,
since sometimes a single oxidation system is not sufcient for the
total decomposition of dyes. These reactions, all of which involve the
accelerated production of the hydroxyl free radical, which is very
reactive, are termed advanced oxidation processes (AOPs) and
include techniques as Fentons reagent oxidation, ultra violet (UV)
photolysis and sonolysis. They are capable of degrading dyes at
ambient temperature and pressure and may also have an advantage
over biological treatment for waste streams containing toxic or bio-
inhibitory contaminants. The central attraction of advanced oxida-
tion processes is that organic contaminants are commonly oxidized
to CO
2
. A wide variety of advanced oxidation processes are available
like chemical oxidation processes using ozone, combined ozone and
peroxide, ultra violet enhanced oxidation such as UV/hydrogen
peroxide, UV/ozone, UV/air wet air oxidation and catalytic wet air
oxidation (where air is used as the oxidant). In a study, Namboodri
and Walsh (1996) reported that when UV process is used alone, only
1020% colour removal was achieved, but when it is used in
conjunction with peroxide, colour removal increased to 90%.
Photo-Fenton process: The combination of Fenton reaction in UV
light, the so-called photo-Fenton reaction, had been shown to
enhance the efciency of the Fenton process and had been found to
be effective in treating dye wastewaters (Bandala et al., 2008). Mur-
uganandham and Swaminathan (2004) studied the photochemical
decolourisation of chlorotriazine reactive azo dye reactive orange 4
by Fenton and photo-Fenton processes. The effects of solution pH,
applied H
2
O
2
, Fe
2
dose, UV light intensity were studied and it was
found that the increase of initial dye concentration decreases the
removal rate. Authors suggested that under optimum conditions the
photo-Fenton process is more efcient than Fenton process.
Photocatalysis is also one of a series of advanced oxidation
processes for pollutant degradation (Aguedach et al., 2005; Akyol
et al., 2004; Arslan-Alaton, 2003; Behnajady et al., 2006; Ghorai
et al., 2007; Gupta et al., 2007a). In photocatalysis, light energy
from a light source excites an electron from the valence band of the
catalyst to the conduction band with a series of reaction which
results in the formation of hydroxyl radicals. The hydroxyl radicals
have high oxidizing potential and therefore can attack most organic
structures causing oxidation. Various chalcogenides (oxides such as
TiO
2
, ZnO, ZrO
2
, CeO
2
, etc. or suldes such as CdS, ZnS, etc.) have
been used, as photocatalysts in the photocatalytic process and the
process is found suitable for a wide range of dyes including direct,
reactive, vat and disperse. Some nice information about the pho-
tocatalytic degradation of azo dyes containing different
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2316
functionalities can be found in review of Konstantinou and Albanis
(2004). The authors suggested that the degradation of dyes depend
on several parameters such as pH, catalyst concentration, substrate
concentration and the presence of electron acceptors such as
hydrogen peroxide and ammonium persulfate besides molecular
oxygen. A study of photocatalytic degradation of methyl orange
(MO) and rhodamine 6 G (R6 G), employing heterogeneous pho-
tocatalytic process, and photocatalytic activity of various semi-
conductors such as titanium dioxide (TiO
2
), zinc oxide (ZnO),
stannic oxide (SnO
2
), zinc sulde (ZnS) and cadmium sulde (CdS)
has been carried out by Kansal et al. (2007). The effect of process
parameters viz., amount of catalyst, concentration of dye and pHon
photocatalytic degradation of MO and R6G was studied. Authors
observed that irradiating the aqueous solutions of dyes containing
photocatalysts with UV and solar light resulted in maximum
decolourization (more than 90%) with ZnO catalyst at basic pH. The
maximum adsorption of MO was noticed at pH 4, and of R6G at pH
10. The percentage reduction of MO and R6G was estimated under
UV/solar systemand it was found that COD reduction takes place at
a faster rate under solar light as compared to UV light. In case of
R6G, highest decolourizing efciency was achieved with lower dose
of catalyst (0.5 g L
1
) than MO (1 g L
1
) under similar conditions.
Authors observed that the performance of photocatalytic system
employing ZnO/solar light was better than ZnO/UV system. Nor-
mally, the advantages of the process are potential of solar light
utilization, no sludge production, considerable reduction of COD.
However, the main drawbacks of process are that there is limitation
of light penetration, fouling of catalysts, and problem of ne cata-
lyst separation from the treated liquid (slurry reactors).
Sonolysis, i.e., use of ultrasonic waves has been used for the
decolourization and degradation of dyes. The mechanism proposed
for the sonochemical processes is usually based on the formation of
short-lived radical species generated in violent cavitation events.
The sonochemical degradation of dyes alizarin and procion blue
was studied by Hong et al. (1999), the authors found the process to
be dependent on ultrasound power and, total solution volume, and
a decrease in reaction rate was observed upon changing the gas
phase in the reactor from air to argon.
The degradation of acid orange 52 in aqueous solutions was
investigated by Maezawa et al. (2007) using three processes viz.
photocatalysis, sonolysis, and photocatalysis with sonication. The
authors found that in the case of photocatalysis, although the
concentration of acid orange 52 decreased to 35% in 480 min,
the colour of the solution did not disappear, while in the case of
sonolysis it decomposed completely in 300 min and the total
organic carbon concentration decreased by only about 13% in
480 min. However, in the case of photocatalysis with sonication,
the concentration of acid orange 52 reached 0 in 240 min and the
total organic carbon concentration decreased by about 87% in
480 min. These results indicate that the ultrasonic irradiation
enhanced the photocatalytic degradation. The authors (Maezawa
et al., 2007) suggested that the photocatalysis with sonication is
most effective for the decomposition of dye in the three processes
studied.
Nevertheless, in general AOPs have the drawback of producing
some undesirable by-products, complete mineralization is not
possible and the process is pH dependent. Also, depending on the
process the limitation may vary, e.g., in the process involving colour
removal by the UV/H
2
O
2
treatment the important factors that
inuence colour removal are peroxide concentration, time of
treatment, intensity of UV radiation, pH, chemical structure of the
dye and dyebath additives. Though the advanced oxidation
processes have proven potential and found technically sound for
colour removal they are quite expensive especially for small-scale
sector of developing countries.
Biological treatment is the most common and widespread
technique used in dye wastewater treatment (Barragan et al., 2007;
Bromley-Challenor et al., 2000; dos Santos et al., 2007; Frijters et al.,
2006; van der Zee and Villaverde, 2005; Zhang et al., 1998). A large
number of species have been used for decolouration and mineral-
ization of various dyes. The methodology offers considerable
advantages like being relatively inexpensive, having low running
costs and the end products of complete mineralization not being
toxic. The process can be aerobic (in presence of oxygen), anaerobic
(without oxygen) or combined aerobicanaerobic.
Aerobic treatment: Bacteria and fungi are the two microorganism
groups that have been most widely studied for their ability to treat
dye wastewaters. In aerobic conditions, enzymes secreted by
bacteria present in the wastewater break down the organic
compounds. The work to identify and isolate aerobic bacteria
capable of degrading various dyes has been going on since more
than two decades (Rai et al., 2005). A number of triphenylmethane
dyes, such as magenta, crystal violet, pararosaniline, brilliant green,
malachite green and ethyl violet, have been found to be efciently
decolourized (92100%) by the strain Kurthia sp. (Sani and Bane-
rjee, 1999b). It was reported by the workers (Sani and Banerjee,
1999b) that after biotransformation, the extent of COD reduction of
the cell free extracts of triphenylmethane dyes was more than 88%
in all dyes except in the case of ethyl violet (70%). Nevertheless, it is
worthwhile pointing that synthetic dyes are not uniformly
susceptible to decomposition by activated sludge in a conventional
aerobic process (Husain, 2006). Attempts to develop aerobic
bacterial strains for dye decolourization often resulted in a specic
strain, which showed a strict ability on a specic dye structure
(Kulla, 1981).
Fungal strains capable of decolourizing azo and triphenyl-
methane dyes have been studied in detail by various workers
(Bumpus and Brock, 1988; Sani and Banerjee, 1999a; Vasdev et al.,
1995). Among various fungi, Phanerochaete chrysosporium, has been
investigated extensively since last two decades for its ability to
decolourize a wide range of dyes by various workers (Fu and Vir-
araghavan, 2001a; Pazarlioglu et al., 2005; Sani and Banerjee,
1999a). Besides this, microorganisms including Rhyzopus oryzae,
Cyathus bulleri, Coriolus versicolour, Funalia trogii, Laetiporous sul-
phureus, Streptomyces sp., Trametes versicolour and other microor-
ganisms have also been tested for the deolorization of dyes (Nigam
et al., 2000; Salony et al., 2006; Zhang et al., 1999). Various factors
like concentration of pollutants, dyestuff concentration, initial pH
and temperature of the efuent, affect the decolourisation process.
It has been suggested that after the fungal treatment, an
improvement in the treatability of the efuent by other microor-
ganisms can be observed (Christie, 2007). Although the treatments
are suitable for some dyes, most of them are recalcitrant to bio-
logical breakdown or are nontransformable under aerobic condi-
tions (Pagga and Brown, 1986; Rai et al., 2005).
Anaerobic Treatment: the potential of anaerobic treatment
applications for the degradation of a wide variety of synthetic dyes
has been well demonstrated and established by (Delee et al., 1998;
Forgacs et al., 2004; Rai et al., 2005). Though some efforts in the
recent past to decolourize dyes under aerobic conditions have met
with success the general perception of nonbiodegradability of most
azo dyes in conventional aerobic systems still persists (Rai et al.,
2005). Since its investigations from early 1970s on anaerobic
decolourization (Rai et al., 2005) of azo dyes various successful
studies have been reported. In a study Razo-Flores et al. (1997)
found that the two azo dyes mordant orange 1 and azodisalicylate
could be reduced and decolourized under anaerobic conditions
using methanogenic granular sludge. Another study (Zee van der
et al., 2001) proved the feasibility of the application of anaerobic
granular sludge for the total decolourization of 20 azo dyes. An
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2317
anaerobic pretreatment (Delee et al., 1998) step could be a cheap
alternative compared with aerobic systems as expensive aeration is
omitted and problems with bulking sludge are avoided. In a review
on anaerobic treatment of textile efuents, Delee et al. (1998)
suggested the advantages of anaerobic treatment to be that dyes
can be reductively decolourised with the efcient and cheap
removal of BOD levels, heavy metals can be retained through
sulfate reduction, no foaming problems with surfactants, high
efuent temperatures can be favourable, high pH efuent can be
acidied and degradation of refractory organics can be initiated
(e.g., surfactants, chlorinated aromatics). Nevertheless, the draw-
backs were suggested (Delee et al., 1998) to be that BOD removal
can be insufcient, dyes and other refractory organics are not
mineralized, nutrients (N, P) are not removed and sulfates give rise
to sulde.
Combined aerobicanaerobic treatment: in order to get better
remediation of coloured compounds from the textile efuents,
a combination of aerobic and anaerobic treatment is suggested to
give encouraging results. An advantage of such system is the
complete mineralization which is often achieved due to the syner-
gistic action of different organisms (Stolz, 2001). Also, the reduction
of the azo bond can be achieved under the reducing conditions in
anaerobic bioreactors (Brown and Laboureur, 1983b) and the
resulting colourless aromatic amines may be mineralized under
aerobic conditions (Brown and Laboureur, 1983a), thereby making
the combined anaerobicaerobic azo dye treatment system attrac-
tive. Thus an anaerobic decolourization followed by aerobic post-
treatment is generally recommended for treating dye wastewaters
(Brown and Hamburger, 1987).
Generally the factors like concentration of dyes, initial pH and
temperature of the efuent, affect the decolourisation process.
Though this methodology is cost-competitive, and biological
treatments are suitable for variety of dyes, the main drawbacks of
the biological treatment is low biodegradability of the dyes, less
exibility in design and operation, larger land area requirement
and longer times required for decolourisationfermentation
processes thereby making it incapable of removing dyes from
efuent on a continuous basis in liquid state fermentations (Bhat-
tacharyya and Sarma, 2003; Crini, 2006; Robinson et al., 2001).
3. Adsorption and ion exchange
In addition to already mentioned methods, the adsorption
process has been widely used for colour removal. Adsorption is one
of the processes, which besides being widely used for dye removal
also has wide applicability in wastewater treatment (Bansal and
Goyal, 2005; Danis et al., 1998; Freeman, 1989; Imamura et al.,
2002; Liapis, 1987; Mantell, 1951; Mattson and Mark, 1971; Pirba-
zari et al., 1991; Quignon et al., 1998; Weber Jr. et al., 1970). The term
adsorption refers to a process wherein a material is concentrated at
a solid surface from its liquid or gaseous surroundings. The history
of carbon adsorption in the purication of water dates back to
ancient times (Cheremisinoff, 2002). Adsorption on porous carbons
was described as early as 1550 B.C. in an ancient Egyptian papyrus
and later by Hippocrates and Pliny the Elder, mainly for medicinal
purposes. However, on scientic records the phenomenon of
adsorption (Mantell, 1951; Tien, 1994) was observed by C.W.
Scheele in 1773 for gases exposed to carbon. This was followed by
observations made by Lowitz in 1785 of the reversible removal of
colour and odour producing compounds from water by wood
charcoal. Larvitz in 1792 and Kehl in 1793 observed similar
phenomenon with vegetable and animal charcoals, respectively.
However, it was Kayser who introduced for the rst time in 1881
the term adsorption to differentiate surface accumulation from
intermolecular penetration. He postulated that the basic feature of
an adsorption process is surface accumulation of material. It is now
customary to differentiate between two types of adsorption. If the
attraction between the solid surface and the adsorbed molecules is
physical in nature, the adsorption is referred to as physical
adsorption (physiosorption). Generally, in physical adsorption the
attractive forces between adsorbed molecules and the solid surface
are van der Waals forces and they being weak in nature result in
reversible adsorption. On the other hand if the attraction forces are
due to chemical bonding, the adsorption process is called chemi-
sorption. In view of the higher strength of the bonding in chemi-
sorption, it is difcult to remove chemisorbed species from the
solid surface.
Ion exchange is basically a reversible chemical process wherein
an ion from solution is exchanged for a similarly charged ion
attached to an immobile solid particle. Ion exchange (LeVan et al.,
1997) shares various common features along with adsorption, in
regard to application in batch and xed-bed processes and they can
be grouped together as sorption processes for a unied treatment
to have high water quality. Ion exchange has been fruitfully used
too for the removal of colours. By far the largest application of ion
exchange (Clifford, 1999) to drinking water treatment is in the area
of softening, that is, the removal of calcium, magnesium, and other
polyvalent cations in exchange for sodium. Various studies have
been carried out using ion exchange for the removal of dyes (Liu
et al., 2007; Raghu and Ahmed Basha, 2007; Wu et al., 2008a).
Delval et al. (2005) prepared starch-based polymers by a cross-
linking reaction of starch-enriched our using epichlorohydrin as
a crosslinking agent in the presence of NH
4
OH. The yield, mobility
and structural properties of crosslinked starch materials with
various compositions were investigated and authors found
a correlation between the structure, mobility and degree of cross-
linking of these sorbents. These crosslinked starch-based materials,
containing tertiary amine groups were used for the recovery of
various dyes from aqueous solutions. The authors suggested that
the sorption mechanism was correlated to the structure of the
polymer.
One of the most important characteristics of an adsorbent is the
quantity of adsorbate it can accumulate which is usually calculated
from the adsorption isotherms. The adsorption isotherms are
constant-temperature equilibrium relationship between the
quantity of adsorbate per unit of adsorbent (q
e
) and its equilibrium
solution concentration (C
e
). Several equations or models are avail-
able that describe this function like the Freundlich and the Lang-
muir equations. Dyes that are difcult to biological breakdown can
often be removed by using the adsorbents. A good adsorbent
(Linsen, 1970; Tien, 1994) should generally possess a porous
structure (resulting in high surface area) and the time taken for
adsorption equilibrium to be established should be as small as
possible so that it can be used to remove dye wastes in lesser time.
Some of the adsorbents, which are generally used for dye
wastewater treatment, are:
Alumina, a synthetic porous crystalline gel, which is available in
the form of granules of different sizes having surface area (Do,
1998) ranging from 200 to 300 m
2
g
1
. Bauxite a naturally occur-
ring porous crystalline alumina contaminated with kaolinite and
iron oxides normally having surface area (Mantell, 1951) ranging
from 25 to 250 m
2
g
1
. Alumina has been studied by various
workers for the removal of dyes (Adak et al., 2005, 2006; Huang
et al., 2007).
Silica Gel, prepared by the coagulation of colloidal silicic acid
results in the formation of porous and noncrystalline granules of
different sizes. It shows a higher surface area (Do, 1998) as
compared to alumina, which ranges from 250 to 900 m
2
g
1
.
Various workers like Alexander and McKay (1977) and Allingham
et al. (1958) investigated the adsorption of basic dyes onto silica,
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2318
although the adsorption capacities were high but the drawback was
that silica is expensive adsorbent (McKay et al., 1999).
Zeolites, are important microporous adsorbents, which are
found naturally and are prepared synthetically too. They are also
considered as selective adsorbents and show ion exchange prop-
erty (Adebajo et al., 2003; Kesraouiouki et al., 1994; Menon and
Komarneni, 1998) as well as molecular adsorption (Caputo and
Pepe, 2007; Curkovic et al., 1997; Kesraouiouki et al., 1994). A
number of zeolites have been used for the removal of dyes (Alpat
et al., 2008; Armagan et al., 2003b; Handreck and Smith, 1988;
Meshko et al., 2001; Nur et al., 2005; Ozdemir et al., 2004; Wang
and Ariyanto, 2007; Wang et al., 2006b,c; Yuan et al., 2007) as well
as for other pollutants too (Ellis and Korth, 1993; Okolo et al., 2000).
Besides zeolites, it was shown in 1934 by Adams and Holmes that
phenol-formaldehyde resins exhibit cation exchange properties.
This led to the development of a different type of resins which are
used as adsorbents through a cation or anion exchange mechanism
like polystyrene sulfonate, sulfonated phenolic resin, phenolic
resin, polystyrene phosphonate, polystyrene amidoxime, poly-
styrene-based trimethyl benzyl ammonium, epoxy-polyamine and
aminopolystyrene. A number of exchange resins have been used
quite efciently for the removal of dyes (Fan et al., 2006; Karcher
et al., 2001, 2002; Yu et al., 2001, 2004; Zhang et al., 2006).
Activated carbon, is the oldest adsorbent known and is usually
prepared from coal, coconut shells, lignite, wood etc., using one of
the two basic activation methods: physical and chemical (Bansal
et al., 1988; Carrott et al., 2003; Hassler, 1963; Lillo-Rodenas et al.,
2007; Phan et al., 2006). Generally, the physical activation requires
high temperature and longer activation time as compared to
chemical activation, however, in chemical activation the AC need
a thorough washing due to the use of chemical agents. A schematic
diagram of the process of producing activated carbons generally
adopted by workers is shown in Fig. 2.
The product formed by either of the methods is known as
activated carbon and normally has a very porous structure with
a large surface area ranging from 500 to 2000 m
2
g
1
(Carrott et al.,
1991). It has been found that adsorption on activated carbon is not
usually selective as it occurs through van der Waals forces. The
ability of charcoal to remove odour and taste was recorded centu-
ries ago. The literature (Freeman, 1989; Tien, 1994) shows that
according to a Sanskrit manuscript from circa 200 BC, It is good to
keep water in copper vessels, to expose it in sunlight and to lter it
through charcoal. However, the credit of developing commercial
activated carbon (Smsek and C
6 10
5
M
24 h 3 Gupta et al. (2006c)
Chitosan Acid red 73 728.2 mg g
1
Wong et al. (2004)
Charnes (raw) Acid red 88
(C.I. 15620)
33.3 mg g
1
60 min 7.02 0.1 Venkata Mohan et al.
(1999)
Lignite coal (raw) Acid red 88
(C.I. 15620)
30.9 mg g
1
60 min 7.02 0.1 Venkata Mohan et al.
(1999)
Bituminous coal (raw) Acid red 88
(C.I. 15620)
26.1 mg g
1
60 min 7.02 0.1 Venkata Mohan et al.
(1999)
Coir pith (raw) Acid violet
(C.I. 42650)
1.65 mg g
1
120 min Namasivayam et al.
(2001a)
Coir pith carbonized Acid violet
(C.I. 42650)
259 m
2
g
1
8.06 mg g
1
40 min Namasivayam et al.
(2001b)
Orange peel (raw) Acid violet 17 19.88 mg g
1
80 min 6.3 Sivaraj et al. (2001)
Fly ash-Czech Republic Acid yellow 11 5.47 m
2
g
1
0.0052 mmol g
1
0.05
0.20 mmol L
1
72 h Janos et al. (2003)
Pine sawdust (raw) Acid yellow 132 398.8 mg g
1
120 min 3.5 Ozacar and Sengil
(2005)
Calcined alunite Acid yellow 17 42.8 m
2
g
1
151.5 mg g
1
25200 mg L
1
90 min 2 Ozacar and Sengil
(2002)
Sawdust carbon Acid yellow 36
(C.I. 13065)
516.3 m
2
g
1
183.8 mg g
1
60 min 3 Malik (2003)
Rice husk carbon Acid yellow 36
(C.I. 13065)
272.5 m
2
g
1
86.9 mg g
1
180 min 3 Malik (2003)
Carbonaceous adsorbent Acid yellow 36
(Metanil yellow)
380 m
2
g
1
211 mg g
1
180 min 7.0 0.5 Jain et al. (2003c)
Blast furnace sludge Acid yellow 36
(Metanil yellow)
28 m
2
g
1
1.4 mg g
1
180 min 7.0 0.5 Jain et al. (2003c)
Treated cotton Acid yellow 99 448 mg g
1
Bouzaida and
Rammah (2002)
Carbonaceous adsorbent Ethyl orange 380 m
2
g
1
198 mg g
1
180 min 7.0 0.5 Jain et al. (2003c)
Blast furnace sludge Ethyl orange 28 m
2
g
1
1.3 mg g
1
180 min 7.0 0.5 Jain et al. (2003c)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2322
Natural coal was studied by Mittal and Venkobachar (1993) for
the removal of two basic dyes, rhodamine B and methylene blue and
acidic dye sandola rhodine. The coal was sulfonated and heated in
a water bath prior to the study. Authors found that the nature of
adsorption of acid dye (sandola rhodine) was physisorptionwhile of
basic dyes (methylene blue and rhodamine B) was not. Coal based
sorbents, namely charnes, lignite coal and bituminous coal, have
been used by Venkata Mohan et al. (2002) who presented results on
the adsorption of colour removal of the trisazo direct dye C.I. direct
brown 1:1 by these adsorbents and compared the results with
activated carbon (Filtrasorb 400). The coal based adsorbents were
found to achieve equilibrium in a short time (60 min) compared to
activated carbon (400 min) which was suggested to be due to the
presence of acidic groups (carboxyl and hydroxyl) present on the
coal based adsorbents and which in turn also resulted in a chemi-
sorption mechanism. The sorptioninteraction of the direct dye onto
the coal based sorbents obeyed a rst-order irreversible rate
equationsuggesting a chemisorptionmechanismwhile onactivated
carbon the data tted a rst-order reversible rate equation indi-
cating physisorption. Coal not being a pure material is suggested to
have a variety of surface properties and in turn sorption properties.
It has also been proposed (Karaca et al., 2004) that the nature of
original vegetation and the physical and chemical changes after
pretreatment usually determines its sorption properties.
Peat is one of the natural materials widely available and studied
as an alternative adsorbent for different pollutants as well as dyes
(Allen et al., 1988a,b, 2004; Ho and McKay, 1998b, 2003; Poots et al.,
1976a; Ramakrishna and Viraraghavan, 1997; Sun and Yang, 2003)
bya number of researchers. It covers 3% of the worlds land area, and
the production of peat for energy use was 70 million m
3
in 2005
(Olsson, 2006), thereby, making it important material. The major
constituents of peat are lignin, cellulose, fulvic and humic acid and
the carbon content is generally just over 50% (http://www.
torvproducenterna.se/english/basic-facts.shtml (accessed20.6.08)).
Peat was used by Poots et al. (1976a) as an adsorbent without any
pretreatment for studying the adsorption of telon blue on it. The
authors found that the performance of peat was signicantly better
than that of wood, referred to above, and achieved an equilibrium
adsorption capacity of 16.3 mg g
1
for particles of size 150250 mm
and with a contact time of 2 h. Like wood, the exhausted peat
adsorbent may be disposed off by burning and the heat used for
steam generation. The same adsorbentadsorbate system was also
studied by McKay and Allen (1980) for assessing parameters inu-
encing the surface mass transfer coefcients during the adsorption
process. Ramakrishna and Viraraghavan (1997) studied the perfor-
mance of peat, slag, bentonite clayandyashfor the removal of acid,
basic and disperse dyes.
Similar to other adsorbents peat can also be modied with some
chemical pretreatment to improve its sorption properties and
selectivity. In a study, Sun and Yang (2003) prepared modied
peatresin by mixing oxidizing peat with polyvinylalcohol and
formaldehyde. The material so prepared was found to have a mac-
roreticular porous structure with enhanced physical characteristics.
Authors found that modied peat can be used for the removal of
a variety of basic dyes, with maximum adsorption capacities for
basic violet 14 and basic green 4 as 400 and 350 mg g
1
, respec-
tively. Nevertheless, the mechanism of adsorption of dyes by peat
has been a matter of considerable debate due to the studies with
different conclusions which are probably due to different peat
types as well as due to difference in sample preparation, and also
due to various pollutant-binding mechanisms involved in the bio-
sorption process.
Chitin and chitosan are mechanically tough polysaccharides
with chemical structures similar to cellulose, studied as adsorbents.
Chitin is a fairly abundant natural biopolymer and is generally
found in the exoskeletons of crabs and other arthropods and also in
the cell wall of some fungi whereas chitosan or glucosamine is
a deacetylated derivative of chitin and can be chemically prepared
from it. Both chitin and chitosan are being used as an attractive
source of adsorbents, especially for metal removal. Nevertheless,
they are versatile materials and have been used successfully for the
removal of dyes (Annadurai, 2000; Annadurai et al., 2008; Cestari
et al., 2008; Chatterjee et al., 2007; Cheung et al., 2007; Chiou et al.,
2004; Chiou and Li, 2003; Hasan et al., 2008; Hu et al., 2006b;
Morais et al., 2007; Niramol et al., 2005; Prado et al., 2004; Ratta-
naphani et al., 2007; Rosa et al., 2008; Sakkayawong et al., 2005;
Wong et al., 2004; Wu et al., 2001a; Yoshida and Takemori, 1997;
Zubieta et al., 2008) and reviewed too (Crini and Badot, 2008).
These materials can be used in different forms, from ake-types to
gels, bead-types or bers. The efciency of chitosan as an adsorbent
to remove acid dyes has been presented by Wong et al. (2004), who
found the maximum adsorption capacities of chitosan for acid
orange 12, acid orange 10, acid red 73 and acid red 18 as 973.3,
922.9, 728.2, and 693.2 mg g
1
, respectively.
In search for alternatives to activated carbon, Figueiredo et al.
(2000, 2005) studied squid, sepia pens and anodonta shells con-
taining chitin as adsorbents for colour removal from textile
wastewaters. The materials were studied with and without chem-
ical treatment, either by demineralization followed by deprotei-
nation, or only by one of the two steps. It was reported by these
authors that chemical treatment of the materials under investiga-
tion enhanced their adsorption capacity which was most probably
due to the increase in the relative chitin content. However, they
suggested that the dye removal was better in continuous operation
in a packed column mainly because of biodegradation. The
adsorption of reactive dyes in neutral solutions using chitosan (Wu
et al., 2000) also showed large adsorption capacities (1000
1100 mg g
1
). In a study Al-Degs et al. (2000) observed the
Table 1 (continued)
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration
range
Contact
time
pH Percentage
adsorption
Source
Fly ash Metomega chrome
orange
0.7428 mg g
1
10 mg L
1
110 min 92.25 Gupta and Shukla
(1996)
Wollastonite Metomega chrome
orange
0.6957 mg g
1
10 mg L
1
150 min 73.04 Gupta and Shukla
(1996)
Kaolnite Metomega chrome
orange
0.6506 mg g
1
10 mg L
1
120 min 84.23 Gupta and Shukla
(1996)
Coal Metomega Chrome
orange
0.7691 mg g
1
10 mg L
1
80 min 97.66 Gupta and Shukla
(1996)
Activated bentonite Sella fast brown H 360.5 mg kg
1
3 h Espantaleon et al.
(2003)
AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon; DTMA dodecyltrimethylammoniumbromide-
modied.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2323
Table 2
Adsorption capacities and other parameters for the removal of basic dyes by commercial activated carbons and other alternative adsorbents.
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration range Contact
time
pH Percentage
adsorption
Source
Commercial AC
(E. Merck India)
Basic blue 9
(Methylene
blue)
980.3 mg g
1
100400 mg L
1
90 min 7.4 Kannan and Sundaram
(2001)
CAC granular Wako
(Wako pure chemicals)
Basic blue 9 1150 m
2
g
1
260 mg g
1
2 h Okada et al. (2003)
CAC ber FE400
(Toho Rayon Co.)
Basic blue 9 1010 m
2
g
1
170 mg g
1
2 h Okada et al. (2003)
CAC felt KF1500
(Toyobo Co.)
Basic blue 9 1480 m
2
g
1
300 mg g
1
2 h Okada et al. (2003)
Activated carbon Basic blue 3 648.6 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
GAC (Miloje Zakic) Basic dye
Maxilon
Goldgelb GL EC
159.0 mg g
1
20200 mg dm
3
410
days
Meshko et al. (2001)
GAC (Miloje Zakic) Basic dye
Maxilon.
Schwarz FBL-01
309.2 mg g
1
50500 mg dm
3
410
days
Meshko et al. (2001)
CAC Merck Basic green 4
(Malachite
green)
765 m
2
g
1
222.22 mg g
1
15 min Malik et al. (2007)
Chemviron F-400 Basic red 22 720 mg g
1
501000 mg dm
3
21 days Allen et al. (2003)
Activated carbon Basic red 22 790 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
PAC Chemviron GW Basic red 46 1026 m
2
g
1
106 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
Chemviron F-400 Basic yellow 21 860 mg g
1
501000 mg dm
3
21 days Allen et al. (2003)
Activated carbon Basic yellow 21 600 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
Activated sludge biomass Basic blue 3 36.5 mg g
1
6 h Chu and Chen (2002a)
Palm-fruit bunch (raw) Basic blue 3 92 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
Activated sludge biomass Basic blue 47 157.5 mg g
1
6 h Chu and Chen (2002a)
Activated sludge biomass Basic blue 54 86.6 mg g
1
6 h Chu and Chen (2002a)
Carbonaceous adsorbent Basic blue 6
(Meldola s blue)
380 m
2
g
1
170 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
Blast furnace (BF) sludge,
BF dust, BF slag
Basic blue 6
(Meldola s blue)
28, 13, 4 m
2
g
1
67, 34, 3.7 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
AC-Pinewood Basic blue 69 902 m
2
g
1
1119 mg g
1
5 days 5.4 Tseng et al. (2003)
Bagasse pith raw Basic blue 69 152 mg g
1
101000 mg dm
3
5 days Chen et al. (2001)
Wood sawdust (raw) Basic blue 69 71.9 mg g
1
8 h Ho and McKay (1998a)
Peat Basic blue 69 195 mg g
1
Ho and McKay (1998b)
Wood Basic blue 69
(Astrazone blue)
100.1 mg g
1
2 h Poots et al. (1978)
Peat Basic blue 69
(Astrazone blue)
0.430.91 g g
1
200 mg dm
3
5 days 4.0
4.3
McKay et al. (1981)
Hardwood sawdust Basic blue 69
(Astrazone blue)
82.2105.7 mg g
1
200 mg dm
3
3 h Asfour et al. (1985)
Activated clay Basic blue 69,
basic red 22
585, 488.4 mg g
1
90.23, 61.78 El-Guendi et al. (El-Guendi
et al., 1995)
Bagasse pith Basic blue 69,
basic red 22
157.4, 76.6 mg g
1
200 mg dm
3
5 days McKay et al. (1997)
AC-Pinewood Basic blue 9 902 m
2
g
1
556 mg g
1
5 days 6.6 Tseng et al. (2003)
AC-Waste newspaper Basic blue 9 1740 m
2
g
1
390 mg g
1
2 h Okada et al. (2003)
Bentonite Basic blue 9
(Methylene
blue)
28 m
2
g
1
1667 mg g
1
1001000 mg L
1
180 min 7.9 Ozacar and Sengil (2006)
Coal Basic blue 9 250 mg g
1
101000 ppm 6 h McKay et al. (1999)
Bark Basic blue 9 914 mg g
1
101000 ppm 6 h McKay et al. (1999)
Rice husk Basic blue 9 312 mg g
1
101000 ppm 6 h McKay et al. (1999)
Cotton waste Basic blue 9 277 mg g
1
101000 ppm 6 h McKay et al. (1999)
Hair Basic blue 9 158 mg g
1
101000 ppm 6 h McKay et al. (1999)
Sewage sludge Basic blue 9 114.94 mg g
1
Otero et al. (2003a)
Bamboo dust carbon Basic blue 9 143.2 mg g
1
100400 mg L
1
40 min 7.2 Kannan and Sundaram
(2001)
Coconut shell carbon Basic blue 9 277.9 mg g
1
100400 mg L
1
90 min 7.2 Kannan and Sundaram
(2001)
Groundnut shell carbon Basic blue 9 164.9 mg g
1
100400 mg L
1
45 min 7.2 Kannan and Sundaram
(2001)
Rice husk carbon Basic blue 9 343.5 mg g
1
100400 mg L
1
40 min 7.2 Kannan and Sundaram
(2001)
Straw carbon Basic blue 9 472.1 mg g
1
100400 mg L
1
35 min 7.2 Kannan and Sundaram
(2001)
Raw Date pits Basic blue 9 80.3 mg g
1
20400 mg L
1
24 h Banat et al. (2003)
AC-Apricot shell Basic blue 9 783 m
2
g
1
4.11 mg g
1
24 h Aygun et al. (2003)
AC-Hazelnut shell Basic blue 9 793 m
2
g
1
8.82 mg g
1
24 h Aygun et al. (2003)
AC-Walnut shell Basic blue 9 774 m
2
g
1
3.53 mg g
1
24 h Aygun et al. (2003)
Fly ash-Slovakia Basic blue 9 3.26 m
2
g
1
0.0046 mmol g
1
0.050.20 mmol L
1
72 h Janos et al. (2003)
Fly ash-Czech Republic Basic blue 9 5.47 m
2
g
1
0.0189 mmol g
1
0.050.20 mmol L
1
72 h Janos et al. (2003)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2324
Table 2 (continued)
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration range Contact
time
pH Percentage
adsorption
Source
Fe(III)/Cr(III) hydroxide Basic blue 9 22.8 mg g
1
Namasivayam and
Sumithra (2005)
Banana peel (raw) Basic blue 9 20.623.5 m
2
g
1
20.8 mg g
1
10120 mg L
1
24 h Annadurai et al. (2002)
Orange peel (raw) Basic blue 9 20.623.5 m
2
g
1
18.6 mg g
1
24 h Annadurai et al. (2002)
Clay Basic blue 9 71 m
2
g
1
300 mg g
1
Bagane and Guiza (2000)
Diatomite Basic blue 9 27.8 m
2
g
1
198 mg g
1
100400 mg dm
3
48 h Al-Ghouti et al. (2003)
Diatomite Basic blue 9 33 m
2
g
1
0.42 mmol g
1
0.131.87 mmol L
1
3 days Shawabkeh and Tutunji
(2003)
Clay Basic blue 9 30 m
2
g
1
6.3 mg g
1
1 h Gurses et al. (2004)
Activated sludge Basic blue 9 256.41 mg g
1
300 min 7 Gulnaz et al. (2004)
Spirodela polyrrhiza
biomass
Basic blue 9 144.93 mg g
1
24 h 9 Waranusantigul et al.
(2003)
Dead fungus
Aspergillus niger
Basic blue 9 10.49
18.54 mg g
1
50 mg L
1
2 days Fu and Viraraghavan (2000)
Living biomass
Aspergillus niger
Basic blue 9 1.17 mg g
1
50 mg L
1
2 days Fu and Viraraghavan (2000)
Neem sawdust Basic blue 9 3.622 mg g
1
12 mg L
1
30 min 7.2 75.47 Khattri and Singh (2000)
Yellow passion fruit Basic blue 9 30 m
2
g
1
44.7 mg g
1
48 h 8 Pavan et al. (2008)
Guava leaf powder Basic blue 9 295 mg g
1
100800 mg dm
3
Ponnusami et al. (2008)
Beer brewery waste Basic blue 9 4.5 m
2
g
1
4.92 mg g
1
24 h 7 Tsai et al. (2008)
Jack fruit peel Basic blue 9
(Methylene
blue)
285.713 mg g
1
35400 mg L
1
180 min Hameed (2009a)
Spent tea leaves Basic blue 9
(Methylene
blue)
300.052 mg g
1
30390 mg L
1
180 min Hameed (2009b)
Sugarcane dust Basic blue 9 3.745 mg g
1
12.0 mg L
1
30 min 78.02 Khattri and Singh (1999)
Carbonaceous adsorbent Basic blue 9
(Methylene
blue)
380 m
2
g
1
92 mg g
1
120 min 6.5
7.5
Jain et al. (2003a)
Blast furnace (BF) sludge,
BF dust, BF slag
Basic blue 9
(Methylene
blue)
28, 13, 4 m
2
g
1
6.4, 3.3, 2.1 mg g
1
120 min 6.5
7.5
Jain et al. (2003a)
Diatomite Basic blue 9
(Methylene
blue)
27.80 m
2
g
1
198 mg g
1
100400 mg dm
3
48 h 11 Al-Ghouti et al. (2003)
Cedar sawdust, crushed brick Basic blue 9
(Methylene
blue)
142.36,
96.41 mg g
1
5 h Hamdaoui (2006)
Fly ash (treated with H
2
SO
4
) Basic blue 9
(Methylene
blue)
6.236 m
2
g
1
0.0021 mmol g
1
2.675 10
5
2.675 10
4
M
72 h Lin et al. (2008)
Fly ash, zeolite,
unburned carbon
Basic blue 9
(Methylene
blue)
15.6, 16.0,
224 m
2
g
1
0.02, 0.045
0.25 mmol g
1
1 10
6
1 10
5
M
100,
400 h
Wang et al. (2005b)
PET carbon Basic blue 9
(Methylene
blue)
33.4 mg g
1
2 h Zhang and Itoh (2003)
Hazelnut shell Basic blue 9 76.9 mg g
1
501000, 50
500 mg L
1
60
180 min
Ferrero (2007)
Saw dust-walnut Basic blue 9 59.17 mg g
1
501000, 50
500 mg L
1
60
180 min
Ferrero (2007)
Saw dust-cherry Basic blue 9 39.84 mg g
1
501000, 50
500 mg L
1
60
180 min
Ferrero (2007)
Saw dust-oak Basic blue 9 29.94 mg g
1
501000, 50
500 mg L
1
60
180 min
Ferrero (2007)
Saw dust-pitch pine Basic blue 9 27.78 mg g
1
501000, 50
500 mg L
1
60
180 min
Ferrero (2007)
Sunower stalk Basic blue 9
(Methylene
blue),
Basic red 9
1.2054 m
2
g
1
205, 317 mg g
1
1002000, 100
2000 mg L
1
5 days 80 Sun and Xu (1997)
Beech sawdust untreated Basic blue 9
(Methylene
blue),
Red basic 22
9.78, 20.2 mg g
1
14 days Batzias and Sidiras (2004)
Zeolite Basic dye
Maxilon
Goldgelb GL EC
14.91 mg g
1
20200 mg dm
3
410
days
Meshko et al. (2001)
Zeolite Basic dye
Maxilon.
Schwarz FBL-01
55.86 mg g
1
50500 mg dm
3
410
days
Meshko et al. (2001)
Sawdust carbon Basic green 4 74.5 mg g
1
50250 mg L
1
Garg et al. (2003)
(continued on next page)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2325
Table 2 (continued)
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration range Contact
time
pH Percentage
adsorption
Source
Neem sawdust Basic green 4 3.42 mg g
1
12 mg L
1
30 min 7.2 71.25 Khattri and Singh (2000)
AC from pine sawdust Basic green 4 1390 m
2
g
1
370.37 mg g
1
502000 mg L
1
3 h Akmil-Basar et al. (2005)
Oil palm trunk ber Basic green 4
(Malachite
green)
149.35 mg g
1
25300 mg L
1
120 min Hameed and El-Khaiary
(2008)
AC-groundnut shell Basic green 4
(Malachite
green)
1114 m
2
g
1
222.22 mg g
1
30 min Malik et al. (2007)
Waste material from paper
industry, pine bark
Basic green 4
(Malachite
green)
100 mg L
1
1 h 98.5, 69.3 Mendez et al. (2007)
Carbonaceous material Basic green 4
(Malachite
green)
629 m
2
g
1
75.08 mg g
1
1 10
4
1 10
3
M
68 h w10066 Gupta et al. (1997)
Sugarcane dust Basic green 4
(Malachite
green)
3.999 mg g
1
12.0 mg L
1
30 min 83.32 Khattri and Singh (1999)
Carbonaceous adsorbent Basic orange 2
(Chrysoidine G)
380 m
2
g
1
75 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
Blast furnace (BF) sludge,
BF dust, BF slag
Basic orange 2
(Chrysoidine G)
28, 13, 4 m
2
g
1
10.1, 5.4,
1.9 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
Tree fern Basic red 13 408 mg g
1
24 h 5 Ho et al. (2005)
Activated sludge Basic red 18 285.71 mg g
1
300 min 7 Gulnaz et al. (2004)
Activated sludge biomass Basic red 18 133.9 mg g
1
6 h Chu and Chen (2002a)
Activated clay Basic red 18 (C.I.
11085)
157 mg g
1
2 h 3 Ho et al. (2001)
Coal Basic red 2 (C.I.
50240)
120 mg g
1
101000 ppm 6 h McKay et al. (1999)
Bark Basic red 2 (C.I.
50240)
1119 mg g
1
101000 ppm 6 h McKay et al. (1999)
Rice husk Basic red 2 (C.I.
50240)
838 mg g
1
101000 ppm 6 h McKay et al. (1999)
Cotton waste Basic red 2 (C.I.
50240)
875 mg g
1
101000 ppm 6 h McKay et al. (1999)
Human Hair Basic red 2 (C.I.
50240)
190 mg g
1
101000 ppm 6 h McKay et al. (1999)
Bentonite Basic red 2 (C.I.
50240)
47.73 m
2
g
1
274 mg g
1
50450 mg L
1
60 min Hu et al. (2006a)
AC-Plum kernel Basic red 22 1162 m
2
g
1
710 mg g
1
4.1 Juang et al. (2002)
Sugar-industry-mud Basic red 22 519 mg g
1
502000 mg L
1
3 days Magdy and Daifullah (1998)
Kudzu Basic red 22 210 mg g
1
501000 mg dm
3
21 days Allen et al. (2003)
Bagasse pith raw Basic red 22 75 mg g
1
101000 mg dm
3
5 days Chen et al. (2001)
Palm-fruit bunch RAW Basic red 22 180 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
AC-Bagasse Basic red 22 (C.I.
11055)
607 m
2
g
1
942 mg g
1
4.1 Juang et al. (2002)
Cane pith Basic red 22 (C.I.
11055)
606.8 m
2
g
1
941.7 mg g
1
5 days 4.1 Juang et al. (2001)
AC-Corncob Basic red 22 (C.I.
11055)
943 m
2
g
1
790 mg g
1
4.1 Juang et al. (2002)
Activated sludge biomass Basic red 29 113.2 mg g
1
6 h Chu and Chen (2002a)
AC sludge based Basic red 46 253 m
2
g
1
188 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
Neem sawdust Basic violet 10 2.355 mg g
1
12 mg L
1
30 min 7.2 49.08 Khattri and Singh (2000)
Fly ash-Slovakia Basic violet 10 3.26 m
2
g
1
0.0040 mmol g
1
0.050.20 mmol L
1
72 h Janos et al. (2003)
Fly ash-Czech Republic Basic violet 10 5.47 m
2
g
1
0.0115 mmol g
1
0.050.20 mmol L
1
72 h Janos et al. (2003)
Banana peel Basic violet 10 20.623.5 m
2
g
1
20.6 mg g
1
10120 mg L
1
24 h Annadurai et al. (2002)
Orange peel Basic violet 10 20.623.5 m
2
g
1
14.3 mg g
1
10120 mg L
1
24 h Annadurai et al. (2002)
Coir pith carbonized Basic violet 10
(Rhodamine B)
259 m
2
g
1
2.56 mg g
1
10 min Namasivayam et al. (2001a)
Coir pith (raw) Basic violet 10
(Rhodamine B)
203.25 mg g
1
120 min Namasivayam et al. (2001a)
Sugarcane dust Basic violet 10
(Rhodamine B)
3.240 mg g
1
12.0 mg L
1
30 min 67.50 Khattri and Singh (1999)
Sewage sludge Basic violet 14
(basic fuchsin)
70127 mg g
1
101000 mg L
1
72 h Seredych and Bandosz
(2007)
Neem sawdust Basic violet 3 3.789 mg g
1
12 mg L
1
30 min 7.2 78.94 Khattri and Singh (2000)
Activated sludge biomass Basic violet 3 113.6 mg g
1
6 h Chu and Chen (2002a)
Carbonaceous adsorbent Basic violet 3
(Crystal violet)
380 m
2
g
1
161 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
Blast furnace (BF) sludge,
BF dust, BF slag
Basic violet 3
(Crystal violet)
28, 13, 4 m
2
g
1
25, 11, 3 mg g
1
120 min 6.5
7.5
Jain et al. (2003b)
Activated sewage sludge Basic violet 3
(Crystal violet)
390 m
2
g
1
270.88 mg g
1
1001000 mg L
1
20 min Otero et al. (2003b)
Pyrolysed sewage sludge Basic violet 3
(Crystal violet)
80 m
2
g
1
184.68 mg g
1
1001000 mg L
1
90 min Otero et al. (2003b)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2326
adsorption capacity of 1111, 434 and 400 mg g
1
for reactive yellow,
reactive black and reactive red, respectively for activated carbon
F400 (Chemviron Carbon, UK) having particle size range of 300
500 mm, and compared it with a different study by Juang et al.
(1997), who also investigated the removal of reactive red, reactive
yellow and reactive black but at a particle size of 250420 mm,
respectively by chitosan and reported value of 380, 179 and
87 mg g
1
for the dyes. Though the adsorption capacities were ne
they were comparatively less than activated carbon. Further, in
a different study on reactive dyes Wu et al. (2000) reported the
usefulness of chitosan. The authors found that the bead type of
chitosan gives a higher capacity for dye than the ake type (by
a factor of 24), however, depending on the source of shery wastes.
A comparison of chitosan akes and beads show that beads can
remove 1103 mg g
1
while akes can remove 293 mg g
1
of reactive
red 222. This is due to the fact that the beads have a greater surface
area than the akes. Similar to other adsorbents in an effort to
increase the efciency of chitosan, Chao et al. (2004) suggested
enzymatic grafting of carboxyl groups onto chitosan, as a means to
confer the ability to adsorb basic dyes on beads. Authors found that
the presence of new functional groups on the surface of beads
resulted in increase of the surface polarity and the density of sorp-
tion sites thereby improving the sorption selectivity for the dye.
Despite its good efciency there are some disadvantages (Crini,
2006; Guibal, 2004; Kumar, 2000; Varma et al., 2004) of using
chitosan like, the adsorption properties depend on the different
sources of chitin, crystallinity, the degree of N-acetylation, molec-
ular weight and solution properties, pH, and vary with afnity for
water, percent deacetylation and content of amino group.
Biomass which is available in large quantities and at low price
has got an increasing interest in dye wastewater treatment. A
number of studies (Akar et al., 2006, 2008; Bakshi et al., 2006;
Banks and Parkinson, 1992; Chu and Chen, 2002a,b; Fu and Virar-
aghavan, 2002a,b, 2000, 2001a; Khalaf, 2008; Low et al., 1995;
Tunali et al., 2007) has been carried out to investigate the ef-
ciencies and mechanism of the removal of dyes by various types of
biomass, and some review on biosorption (Aksu, 2005) too exists.
Biomass of non-living dried roots of water hyacinth (without any
pretreatment) was explored by Lowet al. (1995) as an adsorbent for
the removal of methylene blue and victoria blue and the authors
found that it possessed good adsorptive capacity of 128.9 and
145.4 mg g
1
, for methylene blue and victoria blue, respectively.
Biomass has a high potential as a sorbent due to its physico-
chemical characteristics. Fu and Viraraghavan (2002a,b, 2000,
2001a) investigated the removal of various dyes like, basic blue 9,
acid blue 29, congo red, and disperse red 1 by biosorption on dead
and pretreated Aspergillus niger (A. niger) fungus. The authors found
that A. niger is capable of removing dyes from an aqueous solution
and suggested that three major functional groups: carboxyl, amino
and phosphate, and the lipid fraction in the biomass of A. niger play
an important role in the biosorption of these dyes. A. niger was also
used by Khalaf (2008) who studied the biosorbent for removal of
a reactive dye synazol fromits multi component textile wastewater
and compared it with Spirogyra sp., a fresh water green algae. The
results obtained revealed that dried autoclaved biomass of A. niger
and Spirogyra sp. exhibited maximum dye removal (88 and 85%,
respectively) with conditions of pH 3, temperature 30
C and
8 g L
1
(w/v) biomass concentration after 18 h contact time. It has
been reported that pretreatment autoclaving or chemical treatment
also increases the biosorption capacity (Fu and Viraraghavan,
2001a; Khalaf, 2008).
The decolourization of dyes by biomass involves several
complex mechanisms such as surface adsorption, ion exchange,
complexation (coordination), complexationchelation and micro-
precipitational, however, limited information is available on the
interactions (Banks and Parkinson, 1992; Chu and Chen, 2002a,b)
and more studies are needed to conrm the interactions. Though
biomass and biosorption can be a promising potential alternative to
conventional processes for the removal of dyes (Aksu, 2005; Fu and
Viraraghavan, 2002a,b, 2001b; Kiran et al., 2006; Robinson et al.,
2001), it has some limitations such as, the sorption process is
generally slow, pH dependent, and the efuent treatment by
columns is difcult due to the clogging effect.
Cotton is one of the most important and widely used bers by
humans. Cotton found naturally and consisting cellulose exhibits
excellent physical and chemical properties in terms of stability,
water absorbency and dye removal ability. A study dealing with the
adsorption of dyes in a continuous system on treated cotton was
performed by Bouzaida and Rammah (2002). The authors found the
adsorption capacities of cotton for acid blue 25, acid yellow 99 and
reactive yellow 23 to be 589, 448 and 302 mg g
1
, respectively.
Adsorption behaviour of direct dye on cotton in Aerosol-OT (AOT)
reverse micellar system was studied by Sawada and Ueda (2003),
exhaustion of dye was suggested to be perfect and superior to that
in aqueous system. In a study to evaluate the performance of cotton
waste for dye removal, McKay et al. (1999) found that the cotton
waste had the potential to adsorb 875 and 277 mg g
1
of basic red 2
and basic blue 9, respectively.
Among natural materials clays occupy a prominent position
being low cost, available in abundance and having good sorption
properties. There are various types of clays such as ball clay,
bentonite, commonclay, sepiolite, re clay, fullers earth(attapulgite
and montmorillonite varieties) and kaolin. World production of
bentonite was approximately 11.7 Mt and fullers earth production
was estimated to be 5.61 Mt (http://minerals.usgs.gov/minerals/
pubs/commodity/clays/claysmyb05.pdf (accessed 26.9.07)). Sales
reported by producers for absorbent uses were 3.92 Mt in 2005 and
fullers earth(montmorillonite type) accounted for w68%of the clay
used for absorbents, followed by bentonite and a small amount of
kaolin (http://minerals.usgs.gov/minerals/pubs/commodity/clays/
claysmyb05.pdf (accessed 26.9.07)). In recent years, there has been
an increasing interest in utilizing clay minerals such as bentonite,
kaolinite, diatomite and fullers earth as adsorbents to remove not
only inorganic but also organic molecules. The adsorption efciency
of clays generally result from a net negative charge (McKay et al.,
1985b) on the structure of minerals. This negative charge gives clay
the capability to adsorb positively charged species.
Clay along with other low-cost materials such as bagasse pith
and maize cob, has been used as adsorbent for removal of dyes
astrazon blue, maxilon red and telon blue from aqueous solutions
Table 2 (continued)
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration range Contact
time
pH Percentage
adsorption
Source
Sugarcane dust Basic violet 3
(Crystal violet)
3.798 mg g
1
12.0 mg L
1
30 min 79.13 Khattri and Singh (1999)
Palm-fruit bunch (raw) Basic yellow 21 327 mg g
1
50600 mg dm
3
7 days Nassar and Magdy (1997)
Kudzu Basic yellow 21 160 mg g
1
501000 mg dm
3
21 days Allen et al. (2003)
Activated sludge biomass Basic yellow 24 105.6 mg g
1
Chu and Chen (2002b)
AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2327
Table 3
Adsorption capacities and other parameters for the removal of other dyes (apart from acid and basic dyes) by commercial activated carbons and other alternative adsorbents.
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration
range
Contact
time
pH Percentage
adsorption
Source
PAC Chemviron GW Direct black 168 1026 m
2
g
1
18.7 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
Filtrasorb 400 (Calgon
Corporation)
Direct brown 1 (C.I.No. 30110) 7.69 mg g
1
400 min Venkata Mohan et al.
(2002)
GAC Filtrasorb 400
(Calgon Corporation)
Direct red 28 (C.I. 22120) 13.80 mg g
1
42 h Fu and Viraraghavan
(2002a)
PAC from Filtrasorb 400
(Calgon Corporation)
Direct red 28 (C.I. 22120) 16.81 mg g
1
42 h Fu and Viraraghavan
(2002a)
PAC Chemviron GW Direct red 89 1026 m
2
g
1
8.4 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
CAC Aldrich Reactive red X6BN Sandoz 163 mg g
1
251000 mg L
1
24 h 7 Oliveira et al. (2007b)
Filtrasorb 400 (Chemviron
Carbon UK)
Remazol Golden Yellow,
Remazol Red, Remazol Black B
1100 m
2
g
1
1111, 400,
434 mg g
1
50
1000 mg dm
3
21 days Al-Degs et al. (2000)
AC sludge based Direct black 168 253 m
2
g
1
28.9 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
AC-orange peel Direct blue 86 33.78 mg g
1
25125 mg L
1
180 min 2 Nemr et al. (2009)
Charnes, lignite coal,
bituminous coal
Direct brown (C.I.No. 30110) 6.4, 4.1,
2.04 mg g
1
50 mg L
1
60 min Venkata Mohan et al.
(2002)
Banana pith Direct red 5.92 mg g
1
Namasivayam et al.
(1998)
Fe(III)/Cr(III) hydroxide Direct red 12B 5.0 mg g
1
Namasivayam and
Sumithra (2005)
Biogas residual slurry Direct red 12B 3.46 mg g
1
5.55 Namasivayam and
Yamuna (1995)
Orange peel Direct red 23, Direct red 80 10.72,
21.05 mg g
1
15 min 2 Arami et al. (2005)
Coir pith Direct red 28 6.72 mg g
1
Namasivayam and
Kavitha (2002)
Rice hull ash Direct red 28 236.4 m
2
g
1
171 mg g
1
Chou et al. (2001)
Red mud Direct red 28 4.05 mg g
1
90 min 7.3 Namasivayam and
Arasi (1997)
Dead fungus Aspergillus
niger
Direct red 28 14.16 mg g
1
42 h 6 Fu and Viraraghavan
(2002a)
Banana peel Direct red 28 (Congo red) 20.6
23.5 m
2
g
1
18.2 mg g
1
10120 mg L
1
24 h Annadurai et al.
(2002)
Orange peel Direct red 28 (Congo red) 20.6
23.5 m
2
g
1
14.0 mg g
1
10120 mg L
1
24 h Annadurai et al.
(2002)
Activated red mud Direct red 28 (Congo red) 7.08 mg g
1
1090 mg L
1
90 min Tor and Cengeloglu
(2006)
Chitosan Direct red 28 (congo red) 81.23 mg g
1
12 h 7 Wang and Wang
(2007)
Sunower stalk Direct red 28 (Congo red),
Direct blue
1.2054 m
2
g
1
37.78,
26.84 mg g
1
501000, 50
1000 mg L
1
5 days 80 Sun and Xu (1997)
Crude sewage sludge Direct red 79 5.28 m
2
g
1
19.6 mg g
1
24 h 6.4 Dhaouadi and
MHenni (2008)
Mixture almond shells Direct red 80 10.5 m
2
g
1
22.422 mg g
1
50150 mg L
1
6 Doulati Ardejani et al.
(2008)
Soy meal hull Direct red 80, Direct red 81 0.7623 m
2
g
1
178.57,
120.48 mg g
1
50150 mg L
1
24 h 2 Arami et al. (2006)
Chitosan bead
(chemically
crosslinked)
Direct red 81 2383 mg g
1
5 days 4 Chiou et al. (2004)
AC sludge based Direct red 89 253 m
2
g
1
49.2 mg g
1
30250 mg L
1
2 h Martin et al. (2003)
Powdered activated
sludge
Direct yellow 12 98 mg g
1
24 h Kargi and Ozmihci
(2004)
Palm oil ash Disperse blue, disperse red 49.5, 61.35 mg g
1
60 min 2 Hasnain Isa et al.
(2007)
AC from biomass Euphorbia
rigida
Disperse orange 25 74121 m
2
g
1
118.93 mg g
1
50
125 mg dm
3
7 Gerel et al. (2008)
Modied fungal biomass
(Aspergillus niger)
Disperse red 1 (C.I. 11110) 5.59 mg g
1
13.50 mg L
1
4.0 Fu and Viraraghavan
(2002b)
Modied sepiolite Reactive black 5 50.5 m
2
g
1
120.5 mg g
1
Ozdemir et al. (2004)
Modied zeolite Reactive black 5 11.8 m
2
g
1
60.5 mg g
1
Ozdemir et al. (2004)
Rhizopus arrhizus
biomass
Reactive black 5 588.2 mg g
1
20800 mg L
1
24 h Aksu and Tezer (2000)
Sunower seed shells,
mandarin peelings
Reactive black 5 50 mg L
1
210 min 85, 71 Osma et al. (2007)
High lime y ash Reactive black 5 5.35 m
2
g
1
7.184 mg g
1
5100 mg L
1
60 min 5.64 Eren and Acar (2007)
Biomass chlorella
vulgaris
Reactive black B 555.6 mg g
1
20800 mg L
1
24 h 2 Aksu and Tezer (2005)
Untreated alunite Reactive blue 114 (C.I. 21620) 2.92 mg g
1
120 min 2 Ozacar and Sengil
(2003)
Calcined alunite Reactive blue 114 (C.I. 21620) 66 m
2
g
1
170.7 mg g
1
120 min 2 Ozacar and Sengil
(2003)
Metal hydroxide sludge Reactive Blue 19 275 mg g
1
24 h 4 Santos et al. (2008)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2328
Table 3 (continued)
Material Adsorbate Surface area of
adsorbent
Adsorption
capacity
Concentration
range
Contact
time
pH Percentage
adsorption
Source
Biomass Rhizopus
arrhizus
Reactive blue 19
(C.I. 61200)
90 mg g
1
0500 mg L
1
OMahony et al. (2002)
Activated sludge Reactive blue 2
(C.I. 61211)
250 mg g
1
240 min Aksu (2001)
Chitosan bead (chemically
crosslinked)
Reactive blue2,
reactive red2,
reactive yellow2,
reactive yellow86
2498, 2422, 2436,
1911 mg g
1
5 days 34 Chiou et al. (2004)
Charred dolomite Reactive dye Levax
Brilliant Red E-4BA
36 m
2
g
1
950 mg g
1
100
2000 mg L
1
14 days Walker et al. (2003)
Squid pens Reactive green 12,
Direct green 26
8.82 m
2
g
1
39.8, 4.83 mg g
1
15 days - Figueiredo et al.
(2000)
Sepia pens Reactive green 12,
Direct green 26
4.11 m
2
g
1
3.46, 56.0 mg g
1
15 days Figueiredo et al.
(2000)
Anodonta shell Reactive green 12,
Direct green 26
1.42 m
2
g
1
0.436, 11.3 mg g
1
15 days Figueiredo et al.
(2000)
Biomass rhizopus arrhizus Reactive orange 16
(C.I. 17757)
190 mg g
1
0500 mg L
1
OMahony et al. (2002)
Metal hydroxide sludge Reactive red 120 48.31 mg g
1
10200 mg L
1
7 0.3 Netpradit et al. (2003)
Untreated alunite Reactive red 124
(C.I. 17780)
2.85 mg g
1
120 min 10 Ozacar and Sengil
(2003)
Calcined alunite Reactive red 124
(C.I. 17780)
66 m
2
g
1
153 mg g
1
120 min 10 Ozacar and Sengil
(2003)
Metal hydroxide sludge Reactive red 141 56.18 mg g
1
10200 mg L
1
7 0.3 Netpradit et al. (2003)
Crosslinked chitosan bead Reactive red 189 1936 mg g
1
5 days 3 Chiou and Li (2002)
Non-crosslinked chitosan
bead
Reactive red 189 1189 mg g
1
5 days 6 Chiou and Li (2002)
Metal hydroxide sludge Reactive red 2 62.50 mg g
1
10200 mg L
1
7 0.3 Netpradit et al. (2003)
Chitosan bead (crab) Reactive red 222 1106 mg g
1
3 days Wu et al. (2000)
Chitosan bead (lobster) Reactive red 222 1037 mg g
1
3 days Wu et al. (2000)
Chitosan bead (shrimp) Reactive red 222 1026 mg g
1
3 days Wu et al. (2000)
Chitosan ake (shrimp) Reactive red 222 494 mg g
1
3 days Wu et al. (2000)
Chitosan ake (crab) Reactive red 222 293 mg g
1
3 days Wu et al. (2000)
Modied sepiolite Reactive red 239 50.5 m
2
g
1
108.8 mg g
1
Ozdemir et al. (2004)
Modied zeolite Reactive red 239 11.8 m
2
g
1
111.1 mg g
1
Ozdemir et al. (2004)
Biomass rhizopus arrhizus Reactive red 4 (C.I. 18105) 150 mg g
1
0500 mg L
1
OMahony et al. (2002)
Chromium containing
leather waste
Reactive red X6BN Sandoz 48 mg g
1
251000 mg L
1
24 h 7 Oliveira et al. (2007b)
Modied sepiolite Reactive yellow 176 50.5 m
2
g
1
169.1 mg g
1
Ozdemir et al. (2004)
Modied zeolite Reactive yellow 176 11.8 m
2
g
1
88.5 mg g
1
Ozdemir et al. (2004)
Activated sludge Reactive yellow 2
(CI 18972)
333.3 mg g
1
240 min Aksu (2001)
Treated cotton Reactive yellow 23 302 mg g
1
Bouzaida and
Rammah (2002)
Untreated alunite Reactive yellow 64
(C.I. 29025)
5 mg g
1
120 min 10 Ozacar and Sengil
(2003)
Calcined alunite Reactive yellow 64
(C.I. 29025)
66 m
2
g
1
236 mg g
1
120 min 10 Ozacar and Sengil
(2003)
Eucalyptus bark Remazol BB 90 mg g
1
500 ppm 2.5 Morais et al. (1999)
Yeast (Saccharomyces
cerevisiae)
Remazol black B 88.5 mg g
1
10400 mg L
1
Aksu (2003)
Yeast (Saccharomyces
cerevisiae)
Remazol blue 84.6 mg g
1
10400 mg L
1
Aksu (2003)
Yeast-C. lipolytica Remazol blue 250 mg g
1
100400 mg L
1
96 h 2 Aksu and Donmez
(2003)
Yeast-C. tropicalis Remazol blue 182 mg g
1
100400 mg L
1
96 h 2 Aksu and Donmez
(2003)
Yeast-Candida sp. Remazol blue 167 mg g
1
100400 mg L
1
96 h 2 Aksu and Donmez
(2003)
Yeast-C. quilliermendii Remazol blue 154 mg g
1
100400 mg L
1
96 h 2 Aksu and Donmez
(2003)
Yeast-C. utilis Remazol blue 114 mg g
1
100400 mg L
1
96 h 2 Aksu and Donmez
(2003)
Biomass chlorella
vulgaris
Remazol Golden
Yellow RNL
71.9 mg g
1
10200 mg L
1
24 h 2 Aksu and Tezer (2005)
Yeast (Saccharomyces
cerevisiae)
Remazol red RB 48.8 mg g
1
10400 mg L
1
Aksu (2003)
Biomass chlorella
vulgaris
Remazol red RR 196.1 mg g
1
20800 mg L
1
24 h 2 Aksu and Tezer (2005)
Crude sewage sludge Vat blue 4 5.28 m
2
g
1
248.3 mg g
1
24 h 9.2 Dhaouadi and
MHenni (2008)
AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2329
by Nassar and Elgeundi (1991). Besides determining the adsorption
capacity for each dyeadsorbent system authors determined the
relative costs of dye removal. The authors found the relative cost of
the removal of astrazon blue using natural clay, bagasse pith and
maize cob to be only 1.7%, 3.9% and 4.1% that of carbon, respectively.
The relative cost of the removal of maxilon red using natural clay,
maize cob and bagasse pith was found to be only 2.4%, 8.3% and
10.3% that of carbon, respectively. The relative cost of the removal of
telon blue using maize cob, natural clay and bagasse pith was found
to be only 2.9%, 3.0% and 5.2% that of carbon, respectively. These
results showed that clay is the cheapest among the materials used.
In a study (McKay et al., 1985b) adsorption capacity of fullers earth
for basic and acid blue was reported to be 220 and 120 mg g
1
,
respectively and authors proposed the adsorbent for the treatment
of textile efuents. Al-Ghouti et al. (2003) investigated the removal
of the problematic reactive dyes as well as basic dyes from textile
wastewater by diatomite. The adsorption of dye onto diatomite was
suggested to be dependent on electrostatic interactions (depending
on the pH used). The authors suggested that the adsorption
capacity increases with increase in pH in the case of cationic dyes,
while an opposite effect was observed for anionic dyes.
Further, in a study to compare the adsorption capacity of clays
with activated carbon, Espantaleon et al. (2003) studied the
removal of the anionic dyes acid yellow 194, acid blue 349 and acid
red 423 on natural bentonite and sepiolite and compared it with
activated carbon. The adsorption on sepiolite (98.6, 99.9,
95.2 mg g
1
for acid yellow 194, acid blue 349, acid red 423,
respectively) was found to be higher than on activated carbon (49.2,
68.2, 26.3 mg g
1
) but comparable to that on natural bentonite
(24.9 92.729.1 mg g
1
). High adsorptive capacity (300 mg g
1
) for
the removal of dyes (methylene blue) by clay has been observed by
other workers too (Bagane and Guiza, 2000). Sepiolite was also
used by Alkan et al. (2007) who studied the adsorption kinetics and
thermodynamics of reactive blue 221(anionic dye), onto sepiolite in
aqueous solution by batch method. The experimental results by
workers showed that the acidic pH, increasing initial dye concen-
tration and temperature favours the adsorption. Adsorption kinetic
was suggested to follow pseudo-second-order kinetic model con-
rming the chemisorption of dye onto sepiolite. Authors suggested
that sepiolite could be employed as a low-cost material for the
removal of textile dyes from efuents. Studies show that the
adsorption capabilities of clays are due to a net negative charge on
the silicate minerals which is neutralized by the adsorption of
positively charged cations such as cationic dyes, heavy metals, etc.
The other main reason for the high adsorption capacity (Cadena
et al., 1990) of clays is the large surface areas ranging up to
800 m
2
g
1
, though pH and temperature also play important roles
in determining adsorption capacities. Besides these, various other
studies (Armagan et al., 2003a; Harris et al., 2001; Ogawa et al.,
1996; Ozcan et al., 2006a,b; Ozcan and Ozcan, 2005; Ozcan et al.,
2004b; Rytwo et al., 2002; Wang et al., 2004) on the adsorption of
dyes by kaolinite, montmorillonite, smectites, bentonite are also
available.
Clays can be modied too to improve their sorption capacity by
giving some treatments like replacing cations present in clay
(Cadena et al., 1990), heat treatment (Pradas et al., 1994), acid
treatment (Espantaleon et al., 2003; Ozcan and Ozcan, 2004). In
a work on bentonite Ozcan et al. (2004a) suggested that the surface
of natural bentonite do not make it a more effective adsorbent for
the removal of hydrophobic organic compounds from aqueous
solution due to the electrically charged and hydrophilic character-
istics of the surface. They suggested that natural bentonite may be
modied with large organic cations to produce a Dodecyl-
trimethylammonium bromide-modied bentonite (DTMA-
bentonite) in a manner that signicantly improves its capability of
removing hydrophobic contaminants from water. The authors
compared the results with Na-bentonite and results showed that
Na-bentonite and DTMA-bentonite prepared from low-cost natural
material have suitable adsorption capacity for the removal of acid
blue 193 (AB193) from aqueous solution. However, DTMA-
bentonite showed a higher adsorption capacity toward AB193 than
Na-bentonite. The adsorption capacity of DTMA-bentonite
(740.5 mg g
1
) was found to be around 11 times higher than that of
Na-bentonite (67.1 mg g
1
) at 20
C. Acid blue 193 has also been
removed efciently by Ozcan et al. (2005) by modifying bentonite
using surfactant benzyltrimethylammonium (BTMA) chloride.
Ozcan et al. (2007) also used the surfactant-modied bentonite
(DTMA-bentonite) for the removal of reactive blue 19 fromaqueous
solutions. The batch adsorption capacity was found to be
206.58 mg g
1
for DTMA-bentonite in acidic solutions (pH around
1.5), which was suggested to be due to the strong electrostatic
interactions between its adsorption site and dye anion. The process
was found to obey Langmuir model.
Modied sepiolite has been tested as an adsorbent by Ozdemir
et al. (2004) for azo-reactive dyes. Authors found that the adsorp-
tion capacities can be improved upon modifying their surfaces with
quaternary amines. Clay (montmorillonite) coupled with chitosan
thereby forming biopolymer chitosan/montmorillonite nano-
composites was used by Wang and Wang (2007) to study adsorp-
tion characteristic of congo red. The authors suggested that
compared with chitosan, the nanocomposite had good occulation
ability in aqueous solution, with comparative low cost (thereby
overcoming the high cost of chitosan) and relatively high adsorp-
tion capacity in comparison to pure montmorillonite, which was in
the order 81.23, 12.70, 54.52 mg g
1
for chitosan, chitosan/mont-
morillonite nanocomposites and montmorillonite, respectively.
Besides these various other natural materials such as zeolites
(Armagan et al., 2003b, 2004a,b; Benkli et al., 2005; Karcher et al.,
2001; Ozdemir et al., 2004), pumice powder (Akbal, 2005), starch
(Crini, 2005; Delval et al., 2003) which is also one of the most
abundant biopolymers, have also been studied for the removal of
dyes. Zeolites (Dabrowski, 2001) are the only existing crystalline
materials with a well dened pore structure in the microporous
range. Zeolites used for the removal of dyes have some similarities
to clays, as the adsorption properties of zeolites also result mainly
from their ion-exchange capabilities. Nevertheless, the sorption
mechanism of zeolite particles is complex owing to several reasons
like their porous structure and surface charges. It is also worth to
mention that the removal efciency of zeolites for dyes may not be
as good as that of clay materials, like raw clinoptilolite was not
found suitable for the removal of reactive dyes due to extremely
low sorption capacities (Armagan et al., 2003b, 2004a; Karcher
et al., 2001), similar conclusions have been found by other workers
too (Benkli et al., 2005; Ozdemir et al., 2004). However, the easy
availability and low cost of some may compensate to some extent
for the associated drawbacks. Similar to other adsorbents, some
modications (Armagan et al., 2003b, 2004b) like chemical modi-
cation with quaternary amines can be helpful in increasing the
sorption capacity.
Industrial/agricultural/domestic wastes or by-products: In
addition to the above discussed natural materials, a number of
agricultural wastes/by-products has also been investigated as
adsorbents for the removal of pollutants by a number of workers.
Shells of almond and hazelnut, and poplar and walnut sawdust
were investigated by Aydin et al. (2004) for the removal of acid
green 25 and acid red 183 from aqueous solution. Equilibrium
isotherms were determined and analysed using the Freundlich
equation. Capacities of adsorbent were found to be in the order:
walnut >poplar >almond >hazelnut for acid green 25; and
almond >walnut >poplar >hazelnut for acid red 183, respectively.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2330
In order to explore the potential use of ground hazelnut shells and
sawdust of four wood species, namely walnut, cherry, oak and pitch
pine materials as low-cost adsorbents for methylene blue and acid
blue 25 dye removal from dye house efuents, batch and column
adsorption studies were carried out by Ferrero (2007). The
adsorption kinetics with all adsorbents was found to t a second-
order rate equation better than Lagergrens rst-order model.
Further, the equilibrium data agreed well with Langmuirs model
and higher adsorption capacity (given for mean particle diameter
125 mm in Tables 1 and 2) was observed for hazelnut shells in
comparison to wood sawdust, for both dyes. For methylene blue,
author observed the adsorption capacity to be even higher (due to
the presence of polar functional groups) than that for activated
carbon from the same material which was suggested to be due to
the fact that thermal activation develops a highly microporous
structure, which are unaccessible to large dye molecules and
conversely destroys the functional groups on the surface which are
involved in the adsorption mechanism.
El-Geundi (1991) studied maize cob, an agricultural waste,
without any pretreatment for the removal of two basic dyes;
astrazone blue and maxilon red, and two acid dyes; telon blue and
erinoyl red. The agricultural waste was found to have high
adsorption capacities of 160 and 94.5 mg g
1
for astrozone blue and
maxilon red and low capacities of 47.7 and 41.4 mg g
1
for erinoyl
red and telon blue, respectively. Sunower stalks were studied as
adsorbents (Sun and Xu, 1997) for basic and direct dyes in aqueous
solutions with equilibrium isotherms and kinetic adsorptions. High
adsorption capacities (Table 2) for basic dyes were observed,
compared to direct dyes (Table 3) and authors suggested that since
sunower stalks consist of cellulose it is the polyol structure of
cellulose-based materials that has relatively strong chemical
adsorption of cations such as metal ions and organic bases as well
as physical adsorption of other materials such as acidic and anionic
compounds. The coulombic forces between dye species and nega-
tively charged cellulose in water are the major interactions which
affect the adsorption of dyes on the materials. Shi et al. (1999)
improved the adsorption capacity of sunower stalks by chemically
grafting quaternary ammonium groups on them. The modied
sunower stalks exhibited increased adsorption capacity for
anionic dyes due to the existence of quaternary ammonium ions on
the surface of the residues. The maximum adsorption capacities on
modied sunower stalks were found to be 191.0 and 216.0 mg g
1
for congo red and direct blue, respectively, which were at least four
times higher than that observed on unmodied sunower stalks.
Further, they observed that adsorption rates of two direct dyestuffs
are much higher on the modied residues than on unmodied
ones.
Orange peel waste was studied by Namasivayamet al. (1996) for
the adsorption of congo red, procion orange and rhodamine B dyes.
The process was studied at different concentrations of dyes,
adsorbent dosage, agitation time and pH and was found to obey
both the Langmuir and the Freundlich isotherms. Also, the authors
suggested that acidic pH is favourable for the adsorption for all
three dyes. Orange peel, has also been investigated as an adsorbent
by Sivaraj et al. (2001), for the removal of an acid dye: acid violet 17.
The material is a waste product with practically no cost but its
adsorption capacity of 19.88 mg g
1
makes it an adsorbent of a little
importance for dyes removal from wastewater. Orange peel as LCA
has also been studied by Arami et al. (2005) for the removal of
direct dyes: direct red 23 and direct red 80. The authors investi-
gated the effects of initial dye concentration (50, 75, 100,
125 mg L
1
), pH, mixing rate, contact time, and quantity of orange
peel at 25
C. The adsorption capacity was found to be 10.72 and
21.05 mg g
1
at initial pH 2, for direct red 23 and direct red 80,
respectively. Similar to the study of Namasivayam et al. (1996) in
this study too the process was found to obey Langmuir model
(better than the Freundlich) and acidic pH favoured the adsorption
of both dyes on the adsorbent, however, unlikely to that study here
the adsorption kinetics and the rates of sorption of both dyes were
found to conform to pseudo-second-order model. A numerical
nite element model to simulate the removal of dissolved textile
synthetic dyes from wastewater by orange peel taking into
consideration both the linear and the Langmuir isotherms to
describe adsorption process has been proposed (Ardejani et al.,
2007). The modelling results were compared to those results
obtained from experimental tests for the removal of direct red 23
and direct red 80 dyes from textile wastewater using orange peel
adsorbent. The model predictions somewhat agree with the
experimental measurements.
Batzias and Sidiras (2004) studied that beech saw dust as low-
cost adsorbent for the removal of methylene blue and basic red
22. Further, in order to know the effect of chemical treatment and
to improve its efciency the authors also tested the potential of
the adsorbent by treating it with CaCl
2
(Batzias and Sidiras, 2004)
and using mild acid hydrolysis (Batzias and Sidiras, 2007a) and
found it to increase the adsorption capacity. Besides this, the
simulation studies for effect of pH were also carried out by Batzias
and Sidiras (2007b). The authors determined the point of zero
charge p.z.c. (5.2) of the sawdust and suggested that increase of
the pH enhances the adsorption behaviour. The low adsorption of
methylene blue at acidic pH was suggested to be due to the
presence of excess H
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