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Journal of Environmental Management 90 (2009) 23132342

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Journal of Environmental Management


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Review

Application of low-cost adsorbents for dye removal A review


V.K. Gupta a, *, Suhas b
a
Department of Chemistry, Indian Institute of Technology Roorkee, Roorkee 247 667, India
b
Centro de Qumica de Evora and Departmento de Quimica, Universidade de Evora, Colegio Lus Antonio Verney, 7000-671 Evora, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Dyes are an important class of pollutants, and can even be identied by the human eye. Disposal of dyes
Received 23 June 2008 in precious water resources must be avoided, however, and for that various treatment technologies are in
Received in revised form use. Among various methods adsorption occupies a prominent place in dye removal. The growing
8 November 2008
demand for efcient and low-cost treatment methods and the importance of adsorption has given rise to
Accepted 24 November 2008
Available online 4 March 2009
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
Keywords:
Adsorbents complied in brief. From a comprehensive literature review, it was found that some LCAs, in addition to
Adsorption having wide availability, have fast kinetics and appreciable adsorption capacities too. Advantages and
Dye removal disadvantages of adsorbents, favourable conditions for particular adsorbateadsorbent systems, and
Dyes adsorption capacities of various low-cost adsorbents and commercial activated carbons as available in
Low-cost adsorbents the literature are presented. Conclusions have been drawn from the literature reviewed, and suggestions
Non-conventional adsorbents for future research are proposed.
Wastewater treatment 2008 Elsevier Ltd. All rights reserved.

1. Introduction Neanderthal man about 1,80,000 years ago. However, the rst
known use of an organic colourant was much later, being nearly
Saving water to save the planet and to make the future of 4000 years ago, when the blue dye indigo was found in the
mankind safe is what we need now. With the growth of mankind, wrappings of mummies in Egyptian tombs (Gordon and Gregory,
society, science, technology our world is reaching to new high 1983). Till the late nineteenth century, all the dyes/colourants were
horizons but the cost which we are paying or will pay in near future more or less natural with main sources like plants, insects and
is surely going to be too high. Among the consequences of this rapid mollusks, and were generally prepared on small scale. It was only
growth is environmental disorder with a big pollution problem. after 1856 that with Perkins historic discovery (Hunger, 2003;
Besides other needs the demand for water (Water for People Venkataraman, 1965) of the rst synthetic dye, mauveine, that dyes
Water for Life United Nations World Water Development Report were manufactured synthetically and on a large scale.
UNESCO) has increased tremendously with agricultural, industrial Dye molecules comprise of two key components: the chromo-
and domestic sectors consuming 70, 22 and 8% of the available phores, responsible for producing the colour, and the auxochromes,
fresh water, respectively and this has resulted in the generation of which can not only supplement the chromophore but also render
large amounts of wastewater (Helmer and Hespanhol, 1997; Lehr the molecule soluble in water and give enhanced afnity (to attach)
et al., 1980; Nemerrow, 1978) containing a number of pollutants. toward the bers. Dyes exhibit considerable structural diversity
One of the important class of the pollutants is dyes, and once they and are classied in several ways. These can be classied (Hunger,
enter the water it is no longer good and sometimes difcult to treat 2003) both by their chemical structure and their application to the
as the dyes have a synthetic origin and a complex molecular ber type. Dyes may also be classied on the basis of their solu-
structure which makes them more stable and difcult to be bio- bility: soluble dyes which include acid, mordant, metal complex,
degraded (Forgacs et al., 2004; Rai et al., 2005). direct, basic and reactive dyes; and insoluble dyes including azoic,
Mankind has used dyes for thousands of years (Christie, 2007) sulfur, vat and disperse dyes. Besides this, either a major azo linkage
and the earliest known use of a colourant is believed to be by or an anthraquinone unit also characterizes dyes chemically. It is
worthwhile noting that the azo dyes are the one most widely used
* Corresponding author. Tel.: 91 1332 285801; fax: 91 1332 273560. and accounts 6570% of the total dyes produced. Though, the
E-mail address: vinodfcy@iitr.ernet.in (V.K. Gupta). classication of dyes on basis of structure is an appropriate system

0301-4797/$ see front matter 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jenvman.2008.11.017
2314 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

and has many advantages, like it readily identies dyes as used for silk, wool, and tannin-mordanted cotton. These water-
belonging to a group and having characteristic properties, e.g., azo soluble dyes yield coloured cations in solution and thats why are
dyes (strong, good all-round properties, cost-effective) and called as cationic dyes. The principal chemical classes are dia-
anthraquinone dyes (weak, expensive), there are a manageable zahemicyanine, triarylmethane, cyanine, hemicyanine, thiazine,
number of chemical groups (about a dozen). Besides these, both the oxazine and acridine.
synthetic dye chemist and the dye technologist use this classica- Disperse Dyes: used mainly on polyester and to some extent on
tion most widely. However, the classication based on application nylon, cellulose, cellulose acetate, and acrylic bers. These are
is advantageous before considering chemical structures in detail substantially water-insoluble nonionic dyes used for hydrophobic
because of the complexities of the dye nomenclature from this type bers from aqueous dispersion. They generally contain azo,
of system. It is also worth to point that classication by application anthraquinone, styryl, nitro, and benzodifuranone groups.
is the principal system adopted by the Colour Index (C.I.). In the Direct Dyes: used in the dyeing of cotton and rayon, paper,
present review we will try to use the dye names based on their leather, and, to some extent to nylon. They are water-soluble
application or their C.I. name/number. This system includes the anionic dyes, and, when dyed from aqueous solution in the pres-
name of the dye class, its hue, and a number. A ve digit C.I. number ence of electrolytes have high afnity for cellulosic bers. Generally
is assigned to a dye when its chemical structure has been disclosed the dyes in this class are polyazo compounds, along with some
by the manufacturer. It is also worth to note here that though a dye stilbenes, phthalocyanines and oxazines.
has a C.I. number, the purity and precise chemical constitution may Reactive Dyes: generally used for cotton and other cellulosics,
vary depending upon the name. An example of dye acid blue 92 is but are also used to a small extent on wool and nylon. These dyes
given in Fig. 1 (Sabnis, 2008). form a covalent bond with the ber and contain chromophoric
Some properties of dyes classied on their usage (Christie, 2007; groups such as azo, anthraquinone, triarylmethane, phthalocya-
Hunger, 2003) are discussed in brief here. nine, formazan, oxazine, etc. Their chemical structures are simpler,
Acid Dyes: used for nylon, wool, silk, modied acrylics, and also absorption spectra show narrower absorption bands, and the
to some extent for paper, leather, ink-jet printing, food, and dyeings are brighter making them advantageous over direct dyes.
cosmetics. They are generally water soluble. The principal chemical Solvent Dyes: used for plastics, gasoline, lubricants, oils, and
classes of these dyes are azo (including premetallized), anthraqui- waxes. These dyes are solvent soluble (water insoluble) and generally
none, triphenylmethane, azine, xanthene, nitro and nitroso. nonpolar or little polar, i.e., lacking polar solubilizing groups such as
Cationic (Basic) Dyes: used for paper, polyacrylonitrile, modied sulfonic acid, carboxylic acid, or quaternary ammonium. The prin-
nylons, modied polyesters, cation dyeable polyethylene tere- cipal chemical classes are predominantly azo and anthraquinone, but
phthalate and to some extent in medicine too. Originally they were 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 form a relatively small group of
dyes the low cost 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, coumarin and naphthalimides
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  1051 106 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
Fig. 1. Acid blue 92 (Sabnis, 2008). C.I. Name: C.I. Acid Blue 92. C.I. Number: C.I. 13390.
oral ingestion and inhalation, skin and eye irritation, and skin
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- sensitization leading to problems like skin irritation and skin sensi-
lene sodium; Benzyl Blue R; Benzyl Fast Blue R; Best Acid Blue 3R; Bucacid Fast Wool tization and also due to carcinogenicity (Christie, 2007; Hatch and
Blue R; Coomassie Blue RL. CA Index Name: 2,7-Naphthalenedisulfonic acid, 4- Maibach, 1999; Rai et al., 2005). They impart colour to water which is
hydroxy-5-[[4-(phenylamino) 5-sulfo-1- naphthalenyl]azo]-, trisodium salt. CAS visible to human eye and therefore, highly objectionable on aesthetic
Registry Number: 3861-73-2. Chemical/Dye Class: Azo. Molecular Formula:
C26H16N3O10S3Na3. Molecular Weight: 695.59. Physical Form: Dark bluish-black
grounds. Not only this, they also interfere with the transmission of
powder. Solubility: Soluble in water, acetone; slightly soluble in ethanol, glycerol. UV- light and upset the biological metabolism processes which cause the
Visible (lmax): 571 nm, 585 nm, 580590 nm. destruction of aquatic communities present in ecosystem (Kuo, 1992;
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2315

Walsh et al., 1980). Further, the dyes have a tendency to sequester Filtration technology is an integral component of drinking
metal and may cause microtoxicity to sh and other organisms water and wastewater treatment applications which includes
(Walsh et al., 1980). As such it is important to treat coloured efuents microltration, ultraltration, nanoltration, and reverse osmosis.
for the removal of dyes. This has been investigated for colour removal (Avlonitis et al., 2008;
For this various methodologies have been presented and even Cheremisinoff, 2002). Each membrane process is best suited for
reviewed too (Aksu, 2005; Banat et al., 1996; Crini, 2006; Crini and a particular water treatment function (Cheremisinoff, 2002).
Badot, 2008; Delee et al., 1998; dos Santos et al., 2007; Forgacs et al., Among them, microltration is of not much use for wastewater
2004; Fu and Viraraghavan, 2001a; Hai et al., 2007; Kandelbauer treatment because of its large pore size, and though ultraltration
and Guebitz, 2005; McMullan et al., 2001; Ozyurt and Atacag, 2003; and nanoltration (Cheremisinoff, 2002; Marmagne and Coste,
Pearce et al., 2003; Rai et al., 2005; Robinson et al., 2001; Sanghi 1996) techniques are effective for the removal of all classes of
and Bhattacharya, 2002; Slokar and Majcen Le Marechal, 1998; dyestuffs, dye molecules cause frequent clogging of the membrane
Stolz, 2001; van der Zee and Villaverde, 2005; Vandevivere et al., pores making the separation systems of limited use for textile
1998; Wesenberg et al., 2003; Wojnarovits and Takacs, 2008). Some efuent treatment. The main drawbacks are high working pres-
of these are discussed in the subsequent paragraphs. sures, signicant energy consumption, high cost of membrane and
a relatively short membrane life which makes their use limited for
2. Methods of dye removal treating dye wastewater. Reverse osmosis forces water, under
pressure, through a membrane that is impermeable to most
Few decades earlier, the dyes selection, application and use were contaminants. The membrane is somewhat better at rejecting salts
not given a major consideration with respect to their environmental than it is at rejecting non-ionized weak acids and bases and smaller
impact. Even the chemical composition of half of the dyes used in the organic molecules generally molecular weight below 200. Reverse
industry was estimated to be unknown. With the growing concern on osmosis (Al-Bastaki, 2004; Marcucci et al., 2001; Sostar-Turk et al.,
health mainly on aesthetic grounds, it was more from 80s that people 2005) is effective decolouring and desalting process against the
started paying much attention to the dye wastes too. In the last few most diverse range of dye wastes, and has been successfully
years, however, more information on the environmental conse- employed for recycling. The water produced by reverse osmosis,
quences of dyestuff usage has become available and the dye manu- will be close to pure H2O.
facturers, users and government themselves are taking substantial Chemical treatment of dye wastewater with a coagulating/
measures to treat the dye containing wastewaters. Since initially occulating agent (Shi et al., 2007; Wang et al., 2006a; Zhou et al.,
there was no discharge limit the treatment of dye wastewater started 2008) is one of the robust ways to remove colour. The process
just with some physical treatments such as sedimentation and involves adding agents, such as aluminum (Al3), calcium (Ca2) or
equalisation to maintain the pH, total dissolved solids (TDS) and total ferric (Fe3) ions, to the dye efuent and induces occulation.
suspended solids (TSS) of the discharged water. Later secondary Besides these other agents (Mishra and Bajpai, 2006; Mishra et al.,
treatments such as the use of lter beds for biodegradation and, more 2006; Yue et al., 2008) have also been used for the process.
recently, the introduction of the activated sludge process (aerobic Sometimes combination (Wang et al., 2007) of two may also be
biodegradation) were used to treat the dye wastewater. Normally added to enhance the process. Generally, the process is economi-
industrial-wastewater treatment processes (Perry et al., 1997) consist cally feasible (but sometimes becomes expensive due to the cost of
of following steps like: Pretreatment industrial-wastewater chemicals) with satisfactory removal of disperse, sulfur, and vat
streams prior to discharge to municipal sewerage systems or even to dyes. However, the main drawback of the process is that the nal
a central industrial sewerage system are pretreated doing equal- product is a concentrated sludge produced in large quantities also,
isation, neutralization; then they undergo primary treatment and besides this, the removal is pH dependent (Kace and Linford, 1975;
wastewater is directed toward removal of pollutants with the least Lee et al., 2006). This process is not good for highly soluble dyes and
effort. Suspended solids are removed by either physical or chemical the result with azo, reactive, acid and especially the basic dyes (Hai
separation techniques and handled as concentrated solids; then they et al., 2007; Raghavacharya, 1997) are generally not good.
are given a secondary treatment usually involving microorganisms Oxidation is a method by which wastewater is treated by using
(biological treatment) primarily bacteria which stabilize the waste oxidizing agents. Generally, two forms viz. chemical oxidation and
components. The third step is physicalchemical treatment or UV assisted oxidation using chlorine, hydrogen peroxide, fentons
tertiary treatment and the processes included in this are adsorption, reagent, ozone, or potassium permanganate are used for treating
ion exchange, stripping, chemical oxidation, and membrane separa- the efuents, especially those obtained from primary treatment
tions. All of these are more expensive than biological treatment but (sedimentation). They are among the most commonly used
are used for the removal of pollutants that are not easily removed by methods for decolourisation processes since they require low
biological methods. Though these are generally utilized in series with quantities and short reaction times. They are used to partially or
biological treatment, sometimes they are used as stand-alone completely degrade the dyes (generally to lower molecular weight
processes too. The nal step being the sludge processing and disposal. species such as aldehydes, carboxylates, sulfates and nitrogen).
Dye wastewater are also treated in more or less a similar way, However, a complete oxidation of dye can theoretically reduce the
nevertheless, there is no single standard methodology/treatment complex molecules to carbon dioxide and water. It is worth to note
procedure used for all types of wastes. that pH and catalysts play an important role in oxidation process.
We are classifying the methodologies generally adopted to treat Chlorine is a strong oxidizing agent used and may also be applied
dye wastewater in four categories: (i) physical (ii) chemical (iii) as calcium hypochlorite and sodium hypochlorite. In addition to
biological and (iv) acoustical, radiation, and electrical processes. being the most widely used disinfectant for water treatment, it is
Some of the methodologies lying in above mentioned categories extensively used for reduction of colour like pulp and textile
are discussed in brief in subsequent paragraphs. bleaching. Reactive, acid, direct and metal complex dyes, which are
Sedimentation is the basic form of primary treatment used at water soluble are decolourised readily by hypochlorite, but water-
most municipal and industrial-wastewater treatment facilities insoluble disperse and vat dyes are resistant to decolourisation in this
(Cheremisinoff, 2002). There are a number of process options process (Namboodri et al., 1994a,b). It has been reported that decol-
available to enhance gravity settling of suspended particles, ourisation of reactive dyes generally require long reaction times,
including chemical occulants, sedimentation basins, and clariers. while metal complex dye solution remains partially coloured even
2316 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

after an extended period of treatment. Dyes (Omura, 1994) having extent, which is sufcient for water reuse even in critical conditions
amino or substituted amino groups on a naphthalene ring, are most as dyeing with light tones.
susceptible to chlorine and decolourise more easily than other dyes. Electrochemical methodology (Gupta et al., 2007b; Lin and
Oxidation can be enhanced through control of pH and also by using Peng, 1994) as a tertiary treatment is also used to remove colour.
catalysts, e.g., in the decomposition of metal complex dyes metals, Decolourisation can be achieved either by electro oxidation with
like iron, copper, nickel and chromium, are liberated and these metals non-soluble anodes or by electro-coagulation using consumable
have a catalytic effect that increases decolourisation. Though the use materials. Several anode materials, like iron, conducting polymer
of chlorine gas is a low-cost methodology for decolourising dye a boron doped diamond electrode etc., with different experimental
wastewater, its use causes unavoidable side reactions, producing conditions, have been used successfully in the electro-degradation
organochlorine compounds including toxic trihalomethane, thereby of dyes (Dogan and Turkdemir, 2005; Faouzi et al., 2007; Oliveira
increasing the absorbable organic halogens content of the treated et al., 2007a). A colour removal (Lopes et al., 2004) of 83100% was
water, also the liberation of metals in metal complex dyes may cause observed for Direct Red 80 using three different electrodes: iron,
corrosion in metallic vessels. polypyrrole doped with chromium and boron doped diamond
Hydrogen peroxide (H2O2) is a very pale blue liquid which electrode. This technique is effective in decolourisation of soluble
appears colourless in a dilute solution, slightly more viscous than and insoluble dyes with reduction of COD. It is worthwhile pointing
water. It has strong oxidizing properties and is therefore a powerful that among other variables the rate of colour and organic load
bleaching agent that is used for bleaching paper besides other uses. removal depends, on the anodes material and the working
About 50% of the worlds production of hydrogen peroxide in 1994 potential. Nevertheless, the main drawbacks are high electricity
was used for paper and pulp bleaching (Hage and Lienke, 2006). cost and sludge production and also pollution from chlorinated
Hydrogen peroxide is also used for making peroxidase enzymes, organics, heavy metals due to indirect oxidation.
which are used for decolourisation of dyes (Morita et al., 1996). Advanced Oxidation Processes (AOPs) are the processes
However, the process is pH dependent and produces sludge. involving simultaneous use of more than one oxidation processes,
Fentons reagent, a solution of hydrogen peroxide and an iron since sometimes a single oxidation system is not sufcient for the
catalyst is also used to oxidize dye wastewaters (Meric et al., 2003; total decomposition of dyes. These reactions, all of which involve the
Wang, 2008) and is stronger than hydrogen peroxide. Generally, it is accelerated production of the hydroxyl free radical, which is very
effective (Kim et al., 2004) in decolourization of both soluble and reactive, are termed advanced oxidation processes (AOPs) and
insoluble dyes (acid, reactive, direct, metal complex dyes) though include techniques as Fentons reagent oxidation, ultra violet (UV)
some dyes like vat and disperse were found to be resistant to it, e.g., photolysis and sonolysis. They are capable of degrading dyes at
dyes (Gregor, 1992) like palanil blue 3RT was resistant to Fentons ambient temperature and pressure and may also have an advantage
reagent, dyes like remazol brilliant blue B, sirrus supra blue BBR, over biological treatment for waste streams containing toxic or bio-
indanthrene blue GCD, irgalan blue FGL and helizarin blue BGT, have inhibitory contaminants. The central attraction of advanced oxida-
been reported to be signicantly decolourised. It is to be noted that, tion processes is that organic contaminants are commonly oxidized
not only is colour removed, but chemical oxygen demand (except to CO2. A wide variety of advanced oxidation processes are available
with reactive dyes), total organic carbon and toxicity are also like chemical oxidation processes using ozone, combined ozone and
reduced. The process is also applicable even with high-suspended peroxide, ultra violet enhanced oxidation such as UV/hydrogen
solid concentration and is preferred for wastewater treatment when peroxide, UV/ozone, UV/air wet air oxidation and catalytic wet air
a municipality allows the release of Fentons sludge into sewage. oxidation (where air is used as the oxidant). In a study, Namboodri
From a biological point of view, it is belived that not only the quality and Walsh (1996) reported that when UV process is used alone, only
of the sludge is improved, but the phosphates can also be elimi- 1020% colour removal was achieved, but when it is used in
nated. The main drawbacks are that it is usually effective within conjunction with peroxide, colour removal increased to 90%.
narrow pH range (Cheng et al., 2004) of <3.5, involves sludge Photo-Fenton process: The combination of Fenton reaction in UV
generation and takes longer reaction time. light, the so-called photo-Fenton reaction, had been shown to
Ozonation carried out by ozone generated from oxygen has been enhance the efciency of the Fenton process and had been found to
studied by various workers and has been found to be an very be effective in treating dye wastewaters (Bandala et al., 2008). Mur-
effective way of decolourizing textile efuents (Perkins et al., 1996; uganandham and Swaminathan (2004) studied the photochemical
Soares et al., 2006; Wu et al., 2008b). Sundrarajan et al. (2007) decolourisation of chlorotriazine reactive azo dye reactive orange 4
studied the ozonation for colour removal (reactive dyes) and found by Fenton and photo-Fenton processes. The effects of solution pH,
that colour removal of the efuent can be achieved in 5 min of applied H2O2, Fe2 dose, UV light intensity were studied and it was
contact time for yellow and blue shades at an ozone consumption found that the increase of initial dye concentration decreases the
of 37.5 and 36 mg L1, respectively and suggested that ozonation is removal rate. Authors suggested that under optimum conditions the
efcient in decolourization of exhausted dye bath efuents con- photo-Fenton process is more efcient than Fenton process.
taining conventional reactive dyes. The decolourization of aqueous Photocatalysis is also one of a series of advanced oxidation
C.I. reactive blue 15 was studied by Wu et al. (2008b) in a semibatch processes for pollutant degradation (Aguedach et al., 2005; Akyol
reactor, who found the process to be a pseudo-rst-order reaction et al., 2004; Arslan-Alaton, 2003; Behnajady et al., 2006; Ghorai
with respect to the dye. The authors observed that ozonation also et al., 2007; Gupta et al., 2007a). In photocatalysis, light energy
effectively removed chemical oxygen demand (COD). However, from a light source excites an electron from the valence band of the
some authors reported that ozonation (Snider and Porter, 1974; catalyst to the conduction band with a series of reaction which
Sundrarajan et al., 2007) while removing colour effectively gener- results in the formation of hydroxyl radicals. The hydroxyl radicals
ally does not minimize COD signicantly. In a study, to know the have high oxidizing potential and therefore can attack most organic
possibility of recycling of reactive dye bath for dyeing of cotton structures causing oxidation. Various chalcogenides (oxides such as
fabric after decolouration Senthilkumar and Muthukumar (2007) TiO2, ZnO, ZrO2, CeO2, etc. or suldes such as CdS, ZnS, etc.) have
used ozone. Cold brand reactive dyes namely red 5MR and golden been used, as photocatalysts in the photocatalytic process and the
yellow MR were used and the oxidation was carried out by ozone. process is found suitable for a wide range of dyes including direct,
Authors suggested that ozonation can be used to remove reactive, vat and disperse. Some nice information about the pho-
completely the colour and chemical oxygen demand too to an tocatalytic degradation of azo dyes containing different
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2317

functionalities can be found in review of Konstantinou and Albanis Biological treatment is the most common and widespread
(2004). The authors suggested that the degradation of dyes depend technique used in dye wastewater treatment (Barragan et al., 2007;
on several parameters such as pH, catalyst concentration, substrate Bromley-Challenor et al., 2000; dos Santos et al., 2007; Frijters et al.,
concentration and the presence of electron acceptors such as 2006; van der Zee and Villaverde, 2005; Zhang et al., 1998). A large
hydrogen peroxide and ammonium persulfate besides molecular number of species have been used for decolouration and mineral-
oxygen. A study of photocatalytic degradation of methyl orange ization of various dyes. The methodology offers considerable
(MO) and rhodamine 6 G (R6 G), employing heterogeneous pho- advantages like being relatively inexpensive, having low running
tocatalytic process, and photocatalytic activity of various semi- costs and the end products of complete mineralization not being
conductors such as titanium dioxide (TiO2), zinc oxide (ZnO), toxic. The process can be aerobic (in presence of oxygen), anaerobic
stannic oxide (SnO2), zinc sulde (ZnS) and cadmium sulde (CdS) (without oxygen) or combined aerobicanaerobic.
has been carried out by Kansal et al. (2007). The effect of process Aerobic treatment: Bacteria and fungi are the two microorganism
parameters viz., amount of catalyst, concentration of dye and pH on groups that have been most widely studied for their ability to treat
photocatalytic degradation of MO and R6G was studied. Authors dye wastewaters. In aerobic conditions, enzymes secreted by
observed that irradiating the aqueous solutions of dyes containing bacteria present in the wastewater break down the organic
photocatalysts with UV and solar light resulted in maximum compounds. The work to identify and isolate aerobic bacteria
decolourization (more than 90%) with ZnO catalyst at basic pH. The capable of degrading various dyes has been going on since more
maximum adsorption of MO was noticed at pH 4, and of R6G at pH than two decades (Rai et al., 2005). A number of triphenylmethane
10. The percentage reduction of MO and R6G was estimated under dyes, such as magenta, crystal violet, pararosaniline, brilliant green,
UV/solar system and it was found that COD reduction takes place at malachite green and ethyl violet, have been found to be efciently
a faster rate under solar light as compared to UV light. In case of decolourized (92100%) by the strain Kurthia sp. (Sani and Bane-
R6G, highest decolourizing efciency was achieved with lower dose rjee, 1999b). It was reported by the workers (Sani and Banerjee,
of catalyst (0.5 g L1) than MO (1 g L1) under similar conditions. 1999b) that after biotransformation, the extent of COD reduction of
Authors observed that the performance of photocatalytic system the cell free extracts of triphenylmethane dyes was more than 88%
employing ZnO/solar light was better than ZnO/UV system. Nor- in all dyes except in the case of ethyl violet (70%). Nevertheless, it is
mally, the advantages of the process are potential of solar light worthwhile pointing that synthetic dyes are not uniformly
utilization, no sludge production, considerable reduction of COD. susceptible to decomposition by activated sludge in a conventional
However, the main drawbacks of process are that there is limitation aerobic process (Husain, 2006). Attempts to develop aerobic
of light penetration, fouling of catalysts, and problem of ne cata- bacterial strains for dye decolourization often resulted in a specic
lyst separation from the treated liquid (slurry reactors). strain, which showed a strict ability on a specic dye structure
Sonolysis, i.e., use of ultrasonic waves has been used for the (Kulla, 1981).
decolourization and degradation of dyes. The mechanism proposed Fungal strains capable of decolourizing azo and triphenyl-
for the sonochemical processes is usually based on the formation of methane dyes have been studied in detail by various workers
short-lived radical species generated in violent cavitation events. (Bumpus and Brock, 1988; Sani and Banerjee, 1999a; Vasdev et al.,
The sonochemical degradation of dyes alizarin and procion blue 1995). Among various fungi, Phanerochaete chrysosporium, has been
was studied by Hong et al. (1999), the authors found the process to investigated extensively since last two decades for its ability to
be dependent on ultrasound power and, total solution volume, and decolourize a wide range of dyes by various workers (Fu and Vir-
a decrease in reaction rate was observed upon changing the gas araghavan, 2001a; Pazarlioglu et al., 2005; Sani and Banerjee,
phase in the reactor from air to argon. 1999a). Besides this, microorganisms including Rhyzopus oryzae,
The degradation of acid orange 52 in aqueous solutions was Cyathus bulleri, Coriolus versicolour, Funalia trogii, Laetiporous sul-
investigated by Maezawa et al. (2007) using three processes viz. phureus, Streptomyces sp., Trametes versicolour and other microor-
photocatalysis, sonolysis, and photocatalysis with sonication. The ganisms have also been tested for the deolorization of dyes (Nigam
authors found that in the case of photocatalysis, although the et al., 2000; Salony et al., 2006; Zhang et al., 1999). Various factors
concentration of acid orange 52 decreased to 35% in 480 min, like concentration of pollutants, dyestuff concentration, initial pH
the colour of the solution did not disappear, while in the case of and temperature of the efuent, affect the decolourisation process.
sonolysis it decomposed completely in 300 min and the total It has been suggested that after the fungal treatment, an
organic carbon concentration decreased by only about 13% in improvement in the treatability of the efuent by other microor-
480 min. However, in the case of photocatalysis with sonication, ganisms can be observed (Christie, 2007). Although the treatments
the concentration of acid orange 52 reached 0 in 240 min and the are suitable for some dyes, most of them are recalcitrant to bio-
total organic carbon concentration decreased by about 87% in logical breakdown or are nontransformable under aerobic condi-
480 min. These results indicate that the ultrasonic irradiation tions (Pagga and Brown, 1986; Rai et al., 2005).
enhanced the photocatalytic degradation. The authors (Maezawa Anaerobic Treatment: the potential of anaerobic treatment
et al., 2007) suggested that the photocatalysis with sonication is applications for the degradation of a wide variety of synthetic dyes
most effective for the decomposition of dye in the three processes has been well demonstrated and established by (Delee et al., 1998;
studied. Forgacs et al., 2004; Rai et al., 2005). Though some efforts in the
Nevertheless, in general AOPs have the drawback of producing recent past to decolourize dyes under aerobic conditions have met
some undesirable by-products, complete mineralization is not with success the general perception of nonbiodegradability of most
possible and the process is pH dependent. Also, depending on the azo dyes in conventional aerobic systems still persists (Rai et al.,
process the limitation may vary, e.g., in the process involving colour 2005). Since its investigations from early 1970s on anaerobic
removal by the UV/H2O2 treatment the important factors that decolourization (Rai et al., 2005) of azo dyes various successful
inuence colour removal are peroxide concentration, time of studies have been reported. In a study Razo-Flores et al. (1997)
treatment, intensity of UV radiation, pH, chemical structure of the found that the two azo dyes mordant orange 1 and azodisalicylate
dye and dyebath additives. Though the advanced oxidation could be reduced and decolourized under anaerobic conditions
processes have proven potential and found technically sound for using methanogenic granular sludge. Another study (Zee van der
colour removal they are quite expensive especially for small-scale et al., 2001) proved the feasibility of the application of anaerobic
sector of developing countries. granular sludge for the total decolourization of 20 azo dyes. An
2318 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

anaerobic pretreatment (Delee et al., 1998) step could be a cheap an adsorption process is surface accumulation of material. It is now
alternative compared with aerobic systems as expensive aeration is customary to differentiate between two types of adsorption. If the
omitted and problems with bulking sludge are avoided. In a review attraction between the solid surface and the adsorbed molecules is
on anaerobic treatment of textile efuents, Delee et al. (1998) physical in nature, the adsorption is referred to as physical
suggested the advantages of anaerobic treatment to be that dyes adsorption (physiosorption). Generally, in physical adsorption the
can be reductively decolourised with the efcient and cheap attractive forces between adsorbed molecules and the solid surface
removal of BOD levels, heavy metals can be retained through are van der Waals forces and they being weak in nature result in
sulfate reduction, no foaming problems with surfactants, high reversible adsorption. On the other hand if the attraction forces are
efuent temperatures can be favourable, high pH efuent can be due to chemical bonding, the adsorption process is called chemi-
acidied and degradation of refractory organics can be initiated sorption. In view of the higher strength of the bonding in chemi-
(e.g., surfactants, chlorinated aromatics). Nevertheless, the draw- sorption, it is difcult to remove chemisorbed species from the
backs were suggested (Delee et al., 1998) to be that BOD removal solid surface.
can be insufcient, dyes and other refractory organics are not Ion exchange is basically a reversible chemical process wherein
mineralized, nutrients (N, P) are not removed and sulfates give rise an ion from solution is exchanged for a similarly charged ion
to sulde. attached to an immobile solid particle. Ion exchange (LeVan et al.,
Combined aerobicanaerobic treatment: in order to get better 1997) shares various common features along with adsorption, in
remediation of coloured compounds from the textile efuents, regard to application in batch and xed-bed processes and they can
a combination of aerobic and anaerobic treatment is suggested to be grouped together as sorption processes for a unied treatment
give encouraging results. An advantage of such system is the to have high water quality. Ion exchange has been fruitfully used
complete mineralization which is often achieved due to the syner- too for the removal of colours. By far the largest application of ion
gistic action of different organisms (Stolz, 2001). Also, the reduction exchange (Clifford, 1999) to drinking water treatment is in the area
of the azo bond can be achieved under the reducing conditions in of softening, that is, the removal of calcium, magnesium, and other
anaerobic bioreactors (Brown and Laboureur, 1983b) and the polyvalent cations in exchange for sodium. Various studies have
resulting colourless aromatic amines may be mineralized under been carried out using ion exchange for the removal of dyes (Liu
aerobic conditions (Brown and Laboureur, 1983a), thereby making et al., 2007; Raghu and Ahmed Basha, 2007; Wu et al., 2008a).
the combined anaerobicaerobic azo dye treatment system attrac- Delval et al. (2005) prepared starch-based polymers by a cross-
tive. Thus an anaerobic decolourization followed by aerobic post- linking reaction of starch-enriched our using epichlorohydrin as
treatment is generally recommended for treating dye wastewaters a crosslinking agent in the presence of NH4OH. The yield, mobility
(Brown and Hamburger, 1987). and structural properties of crosslinked starch materials with
Generally the factors like concentration of dyes, initial pH and various compositions were investigated and authors found
temperature of the efuent, affect the decolourisation process. a correlation between the structure, mobility and degree of cross-
Though this methodology is cost-competitive, and biological linking of these sorbents. These crosslinked starch-based materials,
treatments are suitable for variety of dyes, the main drawbacks of containing tertiary amine groups were used for the recovery of
the biological treatment is low biodegradability of the dyes, less various dyes from aqueous solutions. The authors suggested that
exibility in design and operation, larger land area requirement the sorption mechanism was correlated to the structure of the
and longer times required for decolourisationfermentation polymer.
processes thereby making it incapable of removing dyes from One of the most important characteristics of an adsorbent is the
efuent on a continuous basis in liquid state fermentations (Bhat- quantity of adsorbate it can accumulate which is usually calculated
tacharyya and Sarma, 2003; Crini, 2006; Robinson et al., 2001). from the adsorption isotherms. The adsorption isotherms are
constant-temperature equilibrium relationship between the
3. Adsorption and ion exchange quantity of adsorbate per unit of adsorbent (qe) and its equilibrium
solution concentration (Ce). Several equations or models are avail-
In addition to already mentioned methods, the adsorption able that describe this function like the Freundlich and the Lang-
process has been widely used for colour removal. Adsorption is one muir equations. Dyes that are difcult to biological breakdown can
of the processes, which besides being widely used for dye removal often be removed by using the adsorbents. A good adsorbent
also has wide applicability in wastewater treatment (Bansal and (Linsen, 1970; Tien, 1994) should generally possess a porous
Goyal, 2005; Danis et al., 1998; Freeman, 1989; Imamura et al., structure (resulting in high surface area) and the time taken for
2002; Liapis, 1987; Mantell, 1951; Mattson and Mark, 1971; Pirba- adsorption equilibrium to be established should be as small as
zari et al., 1991; Quignon et al., 1998; Weber Jr. et al., 1970). The term possible so that it can be used to remove dye wastes in lesser time.
adsorption refers to a process wherein a material is concentrated at Some of the adsorbents, which are generally used for dye
a solid surface from its liquid or gaseous surroundings. The history wastewater treatment, are:
of carbon adsorption in the purication of water dates back to Alumina, a synthetic porous crystalline gel, which is available in
ancient times (Cheremisinoff, 2002). Adsorption on porous carbons the form of granules of different sizes having surface area (Do,
was described as early as 1550 B.C. in an ancient Egyptian papyrus 1998) ranging from 200 to 300 m2 g1. Bauxite a naturally occur-
and later by Hippocrates and Pliny the Elder, mainly for medicinal ring porous crystalline alumina contaminated with kaolinite and
purposes. However, on scientic records the phenomenon of iron oxides normally having surface area (Mantell, 1951) ranging
adsorption (Mantell, 1951; Tien, 1994) was observed by C.W. from 25 to 250 m2 g1. Alumina has been studied by various
Scheele in 1773 for gases exposed to carbon. This was followed by workers for the removal of dyes (Adak et al., 2005, 2006; Huang
observations made by Lowitz in 1785 of the reversible removal of et al., 2007).
colour and odour producing compounds from water by wood Silica Gel, prepared by the coagulation of colloidal silicic acid
charcoal. Larvitz in 1792 and Kehl in 1793 observed similar results in the formation of porous and noncrystalline granules of
phenomenon with vegetable and animal charcoals, respectively. different sizes. It shows a higher surface area (Do, 1998) as
However, it was Kayser who introduced for the rst time in 1881 compared to alumina, which ranges from 250 to 900 m2 g1.
the term adsorption to differentiate surface accumulation from Various workers like Alexander and McKay (1977) and Allingham
intermolecular penetration. He postulated that the basic feature of et al. (1958) investigated the adsorption of basic dyes onto silica,
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2319

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 Raw material
found naturally and are prepared synthetically too. They are also (coal, coconut shells, lignite)
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; Physical activation Chemical activation
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 Carbonization Mixing precursor with
as for other pollutants too (Ellis and Korth, 1993; Okolo et al., 2000). (600-900C, N2/Ar) chemical
Besides zeolites, it was shown in 1934 by Adams and Holmes that (H3PO4/KOH/NaOH)
phenol-formaldehyde resins exhibit cation exchange properties. Activation
This led to the development of a different type of resins which are (600-1200C, CO2/O2/H2O) Activation
(450-900C, N2)
used as adsorbents through a cation or anion exchange mechanism
like polystyrene sulfonate, sulfonated phenolic resin, phenolic
resin, polystyrene phosphonate, polystyrene amidoxime, poly- Washing and drying Washing and drying
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
Sieving
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 Final
adopted by workers is shown in Fig. 2. Storage
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 m2 g1 (Carrott et al., Fig. 2. Schematic diagram of the process of producing activated carbons generally
1991). It has been found that adsorption on activated carbon is not adopted by workers.
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 They are normally available in sizes of 1.5, 3 and 4 mm diameter. For
according to a Sanskrit manuscript from circa 200 BC, It is good to ACF, the carbon bers are generally prepared from polymeric
keep water in copper vessels, to expose it in sunlight and to lter it precursor materials such as polyacrylonitrile(PAN), cellulose, pitch
through charcoal. However, the credit of developing commercial and polyvinylchloride; of these PAN based carbon bers predomi-
activated carbon (Smsek and Cerny , 1970) goes to Raphael von nate and have good strength and modulus properties, whereas
Ostrejko whose inventions were patented in 1900 and 1901. The carbon ber can be made with a higher modulus, albeit a lower
applicability of activated carbon for water treatment has been strength, using a pitch-based precursor. These carbon bers after
demonstrated by various workers (Stenzel, 1997; Weber Jr. et al., activation using same methodology results in high surface area
1970). Besides these, various authors (Bansal and Goyal, 2005; carbons.
Hassler, 1963) have discussed and summarized in their book the The activated carbons which are used as adsorbents, not only
successful applications of activated carbons. Activated carbon is remove different types of dyes (Al-Degs et al., 2001; DiGiano and
available in two main forms: powdered activated carbon (PAC) and Natter, 1977; Pelekani and Snoeyink, 2000; Walker and Weatherley,
granular activated carbon (GAC). Most of the work on the removal 1999), but also other organic and inorganic pollutants such as metal
of pollutants from water has been on GAC, due to the fact that the ions (Carrott et al., 1998, 1997; Gabaldon et al., 2000; Kuennen et al.,
granular form is more adaptable to continuous contacting and 1992; Macias-Garcia et al., 1993), phenols (Carrott et al., 2005;
there is no need to separate the carbon from the bulk uid. On the Caturla et al., 1988; Mourao et al., 2006; Paprowicz, 1990; Zogorski
other hand, the use of PAC presents some practical problems et al., 1976), pesticides (Hu et al., 1998; Pirbazari et al., 1991; Pir-
because of the requirement to separate the adsorbent from the uid bazari and Weber Jr., 1984), chlorinated hydrocarbons (Urano et al.,
after use. However, in spite of these problems PAC is also used for 1991), humic substances (Lee et al., 1983), PCBs (Pirbazari et al.,
wastewater treatment due to low capital cost and lesser contact 1992), detergents (Bele et al., 1998; Malhas et al., 2002), organic
time requirement (Najm et al., 1991). Besides PAC and GAC two compounds which cause taste and odour (Flentje and Hager, 1964;
other forms of ACs are also available, Activated Carbon Pellet and Lalezary et al., 1986) and many other chemicals and organisms
Activated Carbon Fiber (ACF). The pelletized activated carbons are (Annesini et al., 1987; Carrott et al., 2000; Donati et al., 1994; Giusti
generally prepared from coal where coal is pulverized and reag- et al., 1974; McKay et al., 1985a; Najm et al., 1993; Saito, 1984;
glomerated with suitable binder and then physically activated. Smith, 1991). It is well known that adsorption by activated carbon is
These materials are made especially for use in vapor applications. an effective and commercially applicable method for removing
2320 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

colour and other pollutants from textile and dye wastes. Porter inactive non-living biomass of microbial or plant origin has been
(1972) suggested that carbon adsorption is a complete treatment reviewed by Ahluwalia and Goyal (2007). An application of bio-
for textile water. In order to demonstrate the versatility of activated sorption using fungi, yeasts and bacteria for the removal of organic
carbon, different workers (Al-Degs et al., 2000, 2001; DiGiano and pollutants has been reviewed by Aksu (2005). A nice review has
Natter, 1977; Pelekani and Snoeyink, 2000; Walker and Weatherley, been presented by Crini (2006) regarding the feasibility of various
1999) have used this adsorbent for different types of dyes. McKay non-conventional low-cost adsorbents for removal of dyes, the
(1982) used activated carbon of Filtrasorb type for the removal of possible use of sawdust for removal of various contaminants such
acidic, basic, disperse and direct dyes and found it to be excellent as dyes and metals, has been discussed by Shukla et al. (2002), use
for the removal of all except direct dyes. Walker and Weatherley of polysaccharide based materials as adsorbents have been
(1999) studied the kinetics of acid dye, tectilon red 2B, on GAC. The reviewed by Crini (2005), and application of chitosan for metal
adsorption of three reactive dyes used in textile industry on Fil- removal has been discussed by Gerente et al. (2007). Also, review
trasorb 400 activated carbon was studied by Al-Degs et al. (2000) on waste materials both conventional (from agriculture and wood
and same workers (Al-Degs et al., 2001) further studied various industry) and non-conventional (from municipal and industrial
activated carbons for the removal of cationic dye (methylene blue) activities) for the preparation of AC, that can be applied in various
and anionic dye (reactive black), and reported that there exists aqueous treatment processes to remove organic pollutants, dyes,
a good relationship between performance of activated carbons and volatile organic compounds, and heavy metals has been presented
methylene blue capacity/surface area. by Dias et al. (2007).
Studies have shown that activated carbons are good materials One of the aim of this review is to give a rough idea to the
for the removal of different types of dyes in general but there use is readers of the step-by-step approach of the why, what and how of
sometimes restricted in view of higher cost. Also, the activated the low-cost adsorbents and dye wastewater treatment, besides the
carbons after their use (treatment of wastewater) become critical discussions. Among various ways of treating dye waste-
exhausted and are no longer capable of further adsorbing the dyes. water one can be utilizing as much as possible our resources
Once AC has been exhausted, it has to be regenerated for further including inexpensive waste/little use materials, combining with
use in purifying water and a number of methods like thermal, inexpensive techniques. We aimed to let researchers know more
chemical, oxidation, electrochemical (Freeman, 1989; Hemphill and more about maximum of the materials which can be used as
et al., 1977; Kilduff and King, 1997; Martin and Ng, 1987; Narbaitz adsorbents. Without going into too much detail, a summary of
and Cen, 1994; Newcombe and Drikas, 1993; Notthakum et al., some relevant published data with some of the latest important
1993; Rollar et al., 1982; Taiwo and Adesina, 2005; Zhou and Lei, results and giving a source of up-to-date literature on the adsorp-
2005) are used for this purpose, the most common being thermal. It tion properties of some alternative adsorbents used for acid, basic,
is worthwhile noting that regeneration of activated carbon adds direct and other dyes removal is presented in Tables 13, and some
cost, furthermore, any regeneration process results in a loss of of the results are discussed here.
carbon and the regenerated product may have a slightly lower Natural materials: Natural materials generally used as LCAs are
adsorption capacity in comparison with the virgin activated carbon. the one existing in nature and used as such or with minor treat-
This has resulted in attempts by various workers to prepare low- ment. Some of the materials used are:
cost alternative adsorbents (Ali and Gupta, 2007) which may Wood as an adsorbent was investigated by Poots et al. (1976b,
replace activated carbons in pollution control through adsorption 1978) who studied the removal of acidic (telon blue, i.e., acid blue
process. 25) as well as basic (astrazone blue, i.e., basic blue 69) dyes thereby
making an attempt to overcome the economic disadvantages of
4. Low-cost alternative adsorbents activated carbon. The adsorbent was studied without any
pretreatment and was sieved into different size ranges prior to use.
Natural materials or the wastes/by-products of industries or The kinetics of the process was found to be dependent on the
synthetically prepared materials, which cost less and can be used as particle size, being minimum (>3 h) for small particle size (150
such or after some minor treatment as adsorbents are generally 250 mm) and maximum (>6 h) for large particle sizes (710
called low-cost adsorbents (LCAs). A protocol based on the 1000 mm) in case of acidic dye, however compared to the acid dye
numerous studies for the development, utilization and application the removal of basic dye (astrazone blue) was found to be in less
of low-cost adsorbents generally adopted by researchers has been contact time (2 h). The monolayer coverage of telon dye on wood
suggested by Gupta et al. (in press). The LCAs as reported in liter- varied from 6.95 to 11.56 mg g1 for particle sizes ranging from 710
ature are usually called substitutes for activated carbons because of to 1000 and 150 to 250 mm, respectively. However, a higher
their similar wide use; however, in a broad and clearer way they are adsorption capacity of 100.1 mg g1 for particles of size 150
basically substitutes for all expensive adsorbents. These low-cost 250 mm was observed for basic dye astrazone blue. Authors sug-
alternative adsorbents (Gupta et al., in press) may be classied in gested that because of its low cost the wood adsorbent does not
two ways either (i) on basis of their availability, i.e., (a) Natural need to be regenerated after use and may be disposed off by
materials such as wood, peat, coal, lignite etc. (b) Industrial/Agri- burning and the heat so evolved can be used for generating steam.
cultural/Domestic wastes or by-products such as slag, sludge, y The drawbacks according to the author of the study were longer
ash, bagasse yash, red mud etc and (c) Synthesized products; or contact time (8 h) and also low adsorption capacity of the wood for
(ii) depending on their nature, i.e., (a) Inorganic and (b) Organic. acidic dye telon blue. Morais et al. (1999) used eucalyptus bark
Some review articles discussing low-cost alternative adsorbents without any pretreatment for removing reactive dyes. The
(Ahluwalia and Goyal, 2007; Aksu, 2005; Babel and Kurniawan, adsorption on bark was suggested because of its high tannin
2003; Bailey et al., 1999; Crini, 2005, 2006; Gerente et al., 2007; content (Bailey et al., 1999; Morais et al., 1999), the polyhydroxy
Gupta and Ali, 2002; Mohan and Pittman, 2006; Pollard et al., 1992; polyphenol groups of tannin are thought to be the active species in
Shukla et al., 2002) have already been available. For example, a nice the adsorption process. The process was found to be exothermic
review on the removal of metals by low-cost adsorbents has been and dye adsorption varying from 4 to 90 mg g1, depending on
presented by Bailey et al. (1999), an overview of low-cost adsor- experimental conditions. The higher value of 90 mg g1 was
bents for heavy metal removal has been presented by Babel and observed at pH 2.5 and with 50 g L1 sodium chloride
Kurniawan (2003), and heavy metals removal by metabolically concentration.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2321

Table 1
Adsorption capacities and other parameters for the removal of acid dyes by commercial activated carbons and other alternative adsorbents.

Material Adsorbate Surface area of Adsorption Concentration Contact pH Percentage Source


adsorbent capacity range time adsorption
GAC Filtrasorb 400 Acid blue 40 1100 m2 g1 57.47 mg g1 25200 mg L1 90 min 1 Ozacar and Sengil
(Chemviron Carbon UK) (CI 62125) (2002)
Filtrasorb F 400 Acid blue 80 (1.05 112.3 mg g1 21 days Choy et al. (2000)
1.2)106 m2 kg1
Filtrasorb F 400 Acid red 114 (1.05 103.5 mg g1 21 days Choy et al. (2000)
1.2)106 m2 kg1
Filtrasorb 400, Calgon Acid red 88 109 mg g1 400 min 7.02  0.1 Venkata Mohan et al.
Corporation (C.I. No. 15620) (1999)
1
Filtrasorb F 400 Acid yellow 117 (1.05 155.8 mg g 21 days Choy et al. (2000)
1.2)106 m2 kg1
GAC Filtrasorb 400 Acid yellow 17 1100 m2 g1 133.3 mg g1 25200 mg L1 90 min 1 Ozacar and Sengil
(Chemviron Carbon UK) (C.I. 10310) (2002)
PAC Chemviron GW Acid brown 283 1026 m2 g1 22 mg g1 30250 mg L1 2h Martin et al. (2003)
AC-Charcoal Acid blue 100.9 mg g1 1025 mg dm3 21 days Choy et al. (1999)
(Polar blue)
AC-Charcoal Acid yellow 128.8 mg g1 1025 mg dm3 21 days Choy et al. (1999)
AC-Charcoal Acid red 114 101 mg g1 1025 mg dm3 21 days Choy et al. (1999)
Fly ash-Czech Republic Acid black 26 5.47 m2 g1 0.0033 mmol g1 0.05 72 h Janos et al. (2003)
0.20 mmol L1
AC Rice husk Acid blue 352 m2 g1 50 mg g1 150 ppm 10 h Mohamed (2004)
(CI 73015)
2 1 1
Carbonaceous adsorbent Acid blue 113 380 m g 219 mg g 180 min 7.0  0.5 Jain et al. (2003c)
Blast furnace sludge Acid blue 113 28 m2 g1 2.1 mg g1 180 min 7.0  0.5 Jain et al. (2003c)
DTMA-bentonite Acid blue 193 767 m2 g1 740.5 mg g1 60 min Ozcan et al. (2004a)
Wood sawdust (raw) Acid blue 25 5.92 mg g1 8h Ho and McKay
(1998a)
Modied silica Acid blue 25 187 m2 g1 45.8 mg g1 Phan et al. (2000)
Peat Acid blue 25 12.7 mg g1 Ho and McKay
(1998b)
Treated cotton Acid blue 25 589 mg g1 Bouzaida and
Rammah (2002)
Chitosan/cyclodextrin Acid blue 25 77.4 mg g1 Martel et al. (2001)
material
Hazelnut shell Acid blue 25 60.2 mg g1 50500 mg L1 60 Ferrero (2007)
180 min
1 1
Saw dust-walnut Acid blue 25 36.98 mg g 50500 mg L 60 Ferrero (2007)
180 min
Saw dust-cherry Acid blue 25 31.98 mg g1 50500 mg L1 60 Ferrero (2007)
180 min
Saw dust-oak Acid blue 25 27.85 mg g1 50500 mg L1 60 Ferrero (2007)
180 min
1 1
Saw dust-pitch pine Acid blue 25 26.19 mg g 50500 mg L 60 Ferrero (2007)
180 min
2 1 1
AC-Corncob Acid blue 25 943 m g 1060 mg g 4.1 Juang et al. (2002)
(C.I. No. 62055)
AC-Bagasse Acid blue 25 607 m2 g1 674 mg g1 4.1 Juang et al. (2002)
(C.I. No. 62055)
AC-Plum kernel Acid blue 25 1162 m2 g1 904 mg g1 4.1 Juang et al. (2002)
(C.I. No. 62055)
2 1 1
Cane (bagasse) pith Acid blue 25 606.8 m g 673.6 mg g 5 days 5.9 Juang et al. (2001)
(C.I. No. 62055)
Bagasse pith(raw) Acid blue 25 17.5 mg g1 101000 mg dm3 5 days Chen et al. (2001)
(C.I. No. 62055)
Wood Acid blue 25 3.86.4 m2 g1 7.011.6 mg g1 Poots et al. (1976b)
(Telon blue)
1 3
Maize cob Acid blue 25, 41.4, 47.7 mg g 0.05 dm 5 days El-Geundi and Aly
Acid Red 114 (1992)
1
Pine sawdust (raw) Acid blue 256 280.3 mg g 120 min 3.5 Ozacar and Sengil
(2005)
AC-Pinewood Acid blue 264 902 m2 g1 1176 mg g1 5 days 6.4 Tseng et al. (2003)
Dead fungus Aspergillus Acid blue 29 1.4413.82 mg g1 50 mg L1 30 h Fu and Viraraghavan
niger (2001b)
Living biomass Aspergillus Acid blue 29 6.63 mg g1 50 mg L1 30 h Fu and Viraraghavan
niger (2001b)
1 1
Modied fungal biomass Acid blue 29 17.58 mg g 45.96 mg L 4.0 Fu and Viraraghavan
(Aspergillus niger) (2002b)
Calcined alunite Acid blue 40 42.8 m2 g1 212.8 mg g1 25200 mg L1 90 min 2 Ozacar and Sengil
(2002)
Activated sewage sludge Acid blue 74 390 m2 g1 60.04 mg g1 1001000 mg L1 165 min Otero et al. (2003b)
(Indigo carmine)
2 1 1 1
Pyrolysed sewage sludge Acid blue 74 80 m g 30.82 mg g 1001000 mg L 180 min Otero et al. (2003b)
(Indigo carmine)
(continued on next page)
2322 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

Table 1 (continued )

Material Adsorbate Surface area of Adsorption Concentration Contact pH Percentage Source


adsorbent capacity range time adsorption
AC-Bagasse Acid blue 80 1433 m2 g1 391 mg g1 201050 mg dm3 7.4 Valix et al. (2004)
Activated clay/carbons Acid blue 9 64.7 mg g1 2.5 h 3.0 Ho and Chiang
mixture (2001)
Activated clay Acid blue 9 57.8 mg g1 2h 3.0 Ho et al. (2001)
(C.I. 42090)
Soy meal hull Acid blue 92 0.7623 m2 g1 114.94 mg g1 50150 mg L1 24 h 2 Arami et al. (2006)
Banana pith Acid brilliant blue 4.42 mg g1 Namasivayam et al.
(1998)
Coir pith (raw) Acid brilliant blue 16.67 mg g1 220 min Namasivayam et al.
(C.I. 42645) (2001a)
AC sludge based Acid brown 283 253 m2 g1 20.5 mg g1 30250 mg L1 2h Martin et al. (2003)
Leather industry waste Acid brown dye 2.846.24 mg g1 50125 mg L1 60 min Sekaran et al. (1995)
(bufng dust)
Chitosan Acid green 25 645.1 mg g1 24 h 4.0  0.1 Wong et al. (2004)
Chitosan Acid orange 10 922.9 mg g1 24 h 4.0  0.1 Wong et al. (2004)
AC-Sugarcane bagasse Acid orange 10 790 m2 g1 5.78 mg g1 525 mg dm3 20 h Tsai et al. (2001)
(C.I. 16230)
Chitosan Acid orange 12 973.3 mg g1 24 h 4.0  0.1 Wong et al. (2004)
Banana peel Acid orange 52 20.623.5 m2 g1 21 mg g1 10120 mg L1 24 h Annadurai et al.
(methyl orange) (2002)
Orange peel Acid orange 52 20.623.5 m2 g1 20.5 mg g1 10120 mg L1 24 h Annadurai et al.
(methyl orange) (2002)
2 1 1
Fly ash-Czech Republic Acid orange 7 5.47 m g 0.2364 mmol g 0.05 72 h Janos et al. (2003)
0.20 mmol L1
Chitosan bead (chemically Acid orange12, acid 1954, 1940, 5 days 34 Chiou et al. (2004)
crosslinked) red14, acid orange 7 1940 mg g1
Fly ash-Czech Republic Acid red 1 5.47 m2 g1 0.1405 mmol g1 0.05 72 h Janos et al. (2003)
0.20 mmol L1
1
Sewage sludge Acid red 1 3573 mg g 101000 mg L1 72 h Seredych and
Bandosz (2007)
1 3
Bagasse pith (raw) Acid red 114 20 mg g 101000 mg dm 5 days Chen et al. (2001)
AC from gingelly seed shell Acid red 114 229.65 m2 g1 102.04 mg g1 8h Thinakaran et al.
(2008)
AC from cotton seed shell Acid red 114 124.35 m2 g1 153.85 mg g1 8h Thinakaran et al.
(2008)
2 1 1
AC from pongam seed shell Acid red 114 324.79 m g 204.08 mg g 8h Thinakaran et al.
(2008)
1 3
Bagasse pith Acid red 114, 22.9, 21.7 mg g 200 mg dm 5 days McKay et al. (1997)
Acid blue 25
Soy meal hull Acid red 14 0.7623 m2 g1 109.89 mg g1 50150 mg L1 24 h 2 Arami et al. (2006)
Chitosan Acid red 18 693.2 mg g1 24 h 4.0  0.1 Wong et al. (2004)
Hen feathers Acid red 51 2.314  105 1  105 24 h 3 Gupta et al. (2006c)
mol g1 6  105 M
Chitosan Acid red 73 728.2 mg g1 Wong et al. (2004)
Charnes (raw) Acid red 88 33.3 mg g1 60 min 7.02  0.1 Venkata Mohan et al.
(C.I. 15620) (1999)
Lignite coal (raw) Acid red 88 30.9 mg g1 60 min 7.02  0.1 Venkata Mohan et al.
(C.I. 15620) (1999)
Bituminous coal (raw) Acid red 88 26.1 mg g1 60 min 7.02  0.1 Venkata Mohan et al.
(C.I. 15620) (1999)
1
Coir pith (raw) Acid violet 1.65 mg g 120 min Namasivayam et al.
(C.I. 42650) (2001a)
Coir pith carbonized Acid violet 259 m2 g1 8.06 mg g1 40 min Namasivayam et al.
(C.I. 42650) (2001b)
Orange peel (raw) Acid violet 17 19.88 mg g1 80 min 6.3 Sivaraj et al. (2001)
Fly ash-Czech Republic Acid yellow 11 5.47 m2 g1 0.0052 mmol g1 0.05 72 h Janos et al. (2003)
0.20 mmol L1
Pine sawdust (raw) Acid yellow 132 398.8 mg g1 120 min 3.5 Ozacar and Sengil
(2005)
Calcined alunite Acid yellow 17 42.8 m2 g1 151.5 mg g1 25200 mg L1 90 min 2 Ozacar and Sengil
(2002)
Sawdust carbon Acid yellow 36 516.3 m2 g1 183.8 mg g1 60 min 3 Malik (2003)
(C.I. 13065)
2 1 1
Rice husk carbon Acid yellow 36 272.5 m g 86.9 mg g 180 min 3 Malik (2003)
(C.I. 13065)
2 1 1
Carbonaceous adsorbent Acid yellow 36 380 m g 211 mg g 180 min 7.0  0.5 Jain et al. (2003c)
(Metanil yellow)
Blast furnace sludge Acid yellow 36 28 m2 g1 1.4 mg g1 180 min 7.0  0.5 Jain et al. (2003c)
(Metanil yellow)
Treated cotton Acid yellow 99 448 mg g1 Bouzaida and
Rammah (2002)
2 1 1
Carbonaceous adsorbent Ethyl orange 380 m g 198 mg g 180 min 7.0  0.5 Jain et al. (2003c)
Blast furnace sludge Ethyl orange 28 m2 g1 1.3 mg g1 180 min 7.0  0.5 Jain et al. (2003c)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2323

Table 1 (continued )

Material Adsorbate Surface area of Adsorption Concentration Contact pH Percentage Source


adsorbent capacity range time adsorption
Fly ash Metomega chrome 0.7428 mg g1 10 mg L1 110 min 92.25 Gupta and Shukla
orange (1996)
1 1
Wollastonite Metomega chrome 0.6957 mg g 10 mg L 150 min 73.04 Gupta and Shukla
orange (1996)
Kaolnite Metomega chrome 0.6506 mg g1 10 mg L1 120 min 84.23 Gupta and Shukla
orange (1996)
Coal Metomega Chrome 0.7691 mg g1 10 mg L1 80 min 97.66 Gupta and Shukla
orange (1996)
1
Activated bentonite Sella fast brown H 360.5 mg kg 3h Espantaleon et al.
(2003)

AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon; DTMA dodecyltrimethylammonium bromide-
modied.

Natural coal was studied by Mittal and Venkobachar (1993) for selectivity. In a study, Sun and Yang (2003) prepared modied
the removal of two basic dyes, rhodamine B and methylene blue and peatresin by mixing oxidizing peat with polyvinylalcohol and
acidic dye sandola rhodine. The coal was sulfonated and heated in formaldehyde. The material so prepared was found to have a mac-
a water bath prior to the study. Authors found that the nature of roreticular porous structure with enhanced physical characteristics.
adsorption of acid dye (sandola rhodine) was physisorption while of Authors found that modied peat can be used for the removal of
basic dyes (methylene blue and rhodamine B) was not. Coal based a variety of basic dyes, with maximum adsorption capacities for
sorbents, namely charnes, lignite coal and bituminous coal, have basic violet 14 and basic green 4 as 400 and 350 mg g1, respec-
been used by Venkata Mohan et al. (2002) who presented results on tively. Nevertheless, the mechanism of adsorption of dyes by peat
the adsorption of colour removal of the trisazo direct dye C.I. direct has been a matter of considerable debate due to the studies with
brown 1:1 by these adsorbents and compared the results with different conclusions which are probably due to different peat
activated carbon (Filtrasorb 400). The coal based adsorbents were types as well as due to difference in sample preparation, and also
found to achieve equilibrium in a short time (60 min) compared to due to various pollutant-binding mechanisms involved in the bio-
activated carbon (400 min) which was suggested to be due to the sorption process.
presence of acidic groups (carboxyl and hydroxyl) present on the Chitin and chitosan are mechanically tough polysaccharides
coal based adsorbents and which in turn also resulted in a chemi- with chemical structures similar to cellulose, studied as adsorbents.
sorption mechanism. The sorption interaction of the direct dye on to Chitin is a fairly abundant natural biopolymer and is generally
the coal based sorbents obeyed a rst-order irreversible rate found in the exoskeletons of crabs and other arthropods and also in
equation suggesting a chemisorption mechanism while on activated the cell wall of some fungi whereas chitosan or glucosamine is
carbon the data tted a rst-order reversible rate equation indi- a deacetylated derivative of chitin and can be chemically prepared
cating physisorption. Coal not being a pure material is suggested to from it. Both chitin and chitosan are being used as an attractive
have a variety of surface properties and in turn sorption properties. source of adsorbents, especially for metal removal. Nevertheless,
It has also been proposed (Karaca et al., 2004) that the nature of they are versatile materials and have been used successfully for the
original vegetation and the physical and chemical changes after removal of dyes (Annadurai, 2000; Annadurai et al., 2008; Cestari
pretreatment usually determines its sorption properties. et al., 2008; Chatterjee et al., 2007; Cheung et al., 2007; Chiou et al.,
Peat is one of the natural materials widely available and studied 2004; Chiou and Li, 2003; Hasan et al., 2008; Hu et al., 2006b;
as an alternative adsorbent for different pollutants as well as dyes Morais et al., 2007; Niramol et al., 2005; Prado et al., 2004; Ratta-
(Allen et al., 1988a,b, 2004; Ho and McKay, 1998b, 2003; Poots et al., naphani et al., 2007; Rosa et al., 2008; Sakkayawong et al., 2005;
1976a; Ramakrishna and Viraraghavan, 1997; Sun and Yang, 2003) Wong et al., 2004; Wu et al., 2001a; Yoshida and Takemori, 1997;
by a number of researchers. It covers 3% of the worlds land area, and Zubieta et al., 2008) and reviewed too (Crini and Badot, 2008).
the production of peat for energy use was 70 million m3 in 2005 These materials can be used in different forms, from ake-types to
(Olsson, 2006), thereby, making it important material. The major gels, bead-types or bers. The efciency of chitosan as an adsorbent
constituents of peat are lignin, cellulose, fulvic and humic acid and to remove acid dyes has been presented by Wong et al. (2004), who
the carbon content is generally just over 50% (http://www. found the maximum adsorption capacities of chitosan for acid
torvproducenterna.se/english/basic-facts.shtml (accessed 20.6.08)). orange 12, acid orange 10, acid red 73 and acid red 18 as 973.3,
Peat was used by Poots et al. (1976a) as an adsorbent without any 922.9, 728.2, and 693.2 mg g1, respectively.
pretreatment for studying the adsorption of telon blue on it. The In search for alternatives to activated carbon, Figueiredo et al.
authors found that the performance of peat was signicantly better (2000, 2005) studied squid, sepia pens and anodonta shells con-
than that of wood, referred to above, and achieved an equilibrium taining chitin as adsorbents for colour removal from textile
adsorption capacity of 16.3 mg g1 for particles of size 150250 mm wastewaters. The materials were studied with and without chem-
and with a contact time of 2 h. Like wood, the exhausted peat ical treatment, either by demineralization followed by deprotei-
adsorbent may be disposed off by burning and the heat used for nation, or only by one of the two steps. It was reported by these
steam generation. The same adsorbentadsorbate system was also authors that chemical treatment of the materials under investiga-
studied by McKay and Allen (1980) for assessing parameters inu- tion enhanced their adsorption capacity which was most probably
encing the surface mass transfer coefcients during the adsorption due to the increase in the relative chitin content. However, they
process. Ramakrishna and Viraraghavan (1997) studied the perfor- suggested that the dye removal was better in continuous operation
mance of peat, slag, bentonite clay and y ash for the removal of acid, in a packed column mainly because of biodegradation. The
basic and disperse dyes. adsorption of reactive dyes in neutral solutions using chitosan (Wu
Similar to other adsorbents peat can also be modied with some et al., 2000) also showed large adsorption capacities (1000
chemical pretreatment to improve its sorption properties and 1100 mg g1). In a study Al-Degs et al. (2000) observed the
2324 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

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 Adsorption Concentration range Contact pH Percentage Source
adsorbent capacity time adsorption
Commercial AC Basic blue 9 980.3 mg g1 100400 mg L1 90 min 7.4 Kannan and Sundaram
(E. Merck India) (Methylene (2001)
blue)
CAC granular Wako Basic blue 9 1150 m2 g1 260 mg g1 2h Okada et al. (2003)
(Wako pure chemicals)
CAC ber FE400 Basic blue 9 1010 m2 g1 170 mg g1 2h Okada et al. (2003)
(Toho Rayon Co.)
2 1 1
CAC felt KF1500 Basic blue 9 1480 m g 300 mg g 2h Okada et al. (2003)
(Toyobo Co.)
Activated carbon Basic blue 3 648.6 mg g1 50600 mg dm3 7 days Nassar and Magdy (1997)
GAC (Miloje Zakic) Basic dye 159.0 mg g1 20200 mg dm3 410 Meshko et al. (2001)
Maxilon days
Goldgelb GL EC
GAC (Miloje Zakic) Basic dye 309.2 mg g1 50500 mg dm3 410 Meshko et al. (2001)
Maxilon. days
Schwarz FBL-01
CAC Merck Basic green 4 765 m2 g1 222.22 mg g1 15 min Malik et al. (2007)
(Malachite
green)
Chemviron F-400 Basic red 22 720 mg g1 501000 mg dm3 21 days Allen et al. (2003)
Activated carbon Basic red 22 790 mg g1 50600 mg dm3 7 days Nassar and Magdy (1997)
PAC Chemviron GW Basic red 46 1026 m2 g1 106 mg g1 30250 mg L1 2h Martin et al. (2003)
Chemviron F-400 Basic yellow 21 860 mg g1 501000 mg dm3 21 days Allen et al. (2003)
Activated carbon Basic yellow 21 600 mg g1 50600 mg dm3 7 days Nassar and Magdy (1997)
Activated sludge biomass Basic blue 3 36.5 mg g1 6h Chu and Chen (2002a)
Palm-fruit bunch (raw) Basic blue 3 92 mg g1 50600 mg dm3 7 days Nassar and Magdy (1997)
Activated sludge biomass Basic blue 47 157.5 mg g1 6h Chu and Chen (2002a)
Activated sludge biomass Basic blue 54 86.6 mg g1 6h Chu and Chen (2002a)
Carbonaceous adsorbent Basic blue 6 380 m2 g1 170 mg g1 120 min 6.5 Jain et al. (2003b)
(Meldolas blue) 7.5
Blast furnace (BF) sludge, Basic blue 6 28, 13, 4 m2 g1 67, 34, 3.7 mg g1 120 min 6.5 Jain et al. (2003b)
BF dust, BF slag (Meldolas blue) 7.5
AC-Pinewood Basic blue 69 902 m2 g1 1119 mg g1 5 days 5.4 Tseng et al. (2003)
Bagasse pith raw Basic blue 69 152 mg g1 101000 mg dm3 5 days Chen et al. (2001)
Wood sawdust (raw) Basic blue 69 71.9 mg g1 8h Ho and McKay (1998a)
Peat Basic blue 69 195 mg g1 Ho and McKay (1998b)
Wood Basic blue 69 100.1 mg g1 2h Poots et al. (1978)
(Astrazone blue)
Peat Basic blue 69 0.430.91 g g1 200 mg dm3 5 days 4.0 McKay et al. (1981)
(Astrazone blue) 4.3
Hardwood sawdust Basic blue 69 82.2105.7 mg g1 200 mg dm3 3h Asfour et al. (1985)
(Astrazone blue)
1
Activated clay Basic blue 69, 585, 488.4 mg g 90.23, 61.78 El-Guendi et al. (El-Guendi
basic red 22 et al., 1995)
Bagasse pith Basic blue 69, 157.4, 76.6 mg g1 200 mg dm3 5 days McKay et al. (1997)
basic red 22
AC-Pinewood Basic blue 9 902 m2 g1 556 mg g1 5 days 6.6 Tseng et al. (2003)
AC-Waste newspaper Basic blue 9 1740 m2 g1 390 mg g1 2h Okada et al. (2003)
Bentonite Basic blue 9 28 m2 g1 1667 mg g1 1001000 mg L1 180 min 7.9 Ozacar and Sengil (2006)
(Methylene
blue)
Coal Basic blue 9 250 mg g1 101000 ppm 6h McKay et al. (1999)
Bark Basic blue 9 914 mg g1 101000 ppm 6h McKay et al. (1999)
Rice husk Basic blue 9 312 mg g1 101000 ppm 6h McKay et al. (1999)
Cotton waste Basic blue 9 277 mg g1 101000 ppm 6h McKay et al. (1999)
Hair Basic blue 9 158 mg g1 101000 ppm 6h McKay et al. (1999)
Sewage sludge Basic blue 9 114.94 mg g1 Otero et al. (2003a)
Bamboo dust carbon Basic blue 9 143.2 mg g1 100400 mg L1 40 min 7.2 Kannan and Sundaram
(2001)
Coconut shell carbon Basic blue 9 277.9 mg g1 100400 mg L1 90 min 7.2 Kannan and Sundaram
(2001)
Groundnut shell carbon Basic blue 9 164.9 mg g1 100400 mg L1 45 min 7.2 Kannan and Sundaram
(2001)
1 1
Rice husk carbon Basic blue 9 343.5 mg g 100400 mg L 40 min 7.2 Kannan and Sundaram
(2001)
Straw carbon Basic blue 9 472.1 mg g1 100400 mg L1 35 min 7.2 Kannan and Sundaram
(2001)
Raw Date pits Basic blue 9 80.3 mg g1 20400 mg L1 24 h Banat et al. (2003)
AC-Apricot shell Basic blue 9 783 m2 g1 4.11 mg g1 24 h Aygun et al. (2003)
AC-Hazelnut shell Basic blue 9 793 m2 g1 8.82 mg g1 24 h Aygun et al. (2003)
AC-Walnut shell Basic blue 9 774 m2 g1 3.53 mg g1 24 h Aygun et al. (2003)
Fly ash-Slovakia Basic blue 9 3.26 m2 g1 0.0046 mmol g1 0.050.20 mmol L1 72 h Janos et al. (2003)
Fly ash-Czech Republic Basic blue 9 5.47 m2 g1 0.0189 mmol g1 0.050.20 mmol L1 72 h Janos et al. (2003)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2325

Table 2 (continued )

Material Adsorbate Surface area of Adsorption Concentration range Contact pH Percentage Source
adsorbent capacity time adsorption
Fe(III)/Cr(III) hydroxide Basic blue 9 22.8 mg g1 Namasivayam and
Sumithra (2005)
2 1 1 1
Banana peel (raw) Basic blue 9 20.623.5 m g 20.8 mg g 10120 mg L 24 h Annadurai et al. (2002)
Orange peel (raw) Basic blue 9 20.623.5 m2 g1 18.6 mg g1 24 h Annadurai et al. (2002)
Clay Basic blue 9 71 m2 g1 300 mg g1 Bagane and Guiza (2000)
Diatomite Basic blue 9 27.8 m2 g1 198 mg g1 100400 mg dm3 48 h Al-Ghouti et al. (2003)
Diatomite Basic blue 9 33 m2 g1 0.42 mmol g1 0.131.87 mmol L1 3 days Shawabkeh and Tutunji
(2003)
Clay Basic blue 9 30 m2 g1 6.3 mg g1 1h Gurses et al. (2004)
Activated sludge Basic blue 9 256.41 mg g1 300 min 7 Gulnaz et al. (2004)
Spirodela polyrrhiza Basic blue 9 144.93 mg g1 24 h 9 Waranusantigul et al.
biomass (2003)
Dead fungus Basic blue 9 10.49 50 mg L1 2 days Fu and Viraraghavan (2000)
Aspergillus niger 18.54 mg g1
Living biomass Basic blue 9 1.17 mg g1 50 mg L1
2 days Fu and Viraraghavan (2000)
Aspergillus niger
1 1
Neem sawdust Basic blue 9 3.622 mg g 12 mg L 30 min 7.2 75.47 Khattri and Singh (2000)
Yellow passion fruit Basic blue 9 30 m2 g1 44.7 mg g1 48 h 8 Pavan et al. (2008)
Guava leaf powder Basic blue 9 295 mg g1 100800 mg dm3 Ponnusami et al. (2008)
Beer brewery waste Basic blue 9 4.5 m2 g1 4.92 mg g1 24 h 7 Tsai et al. (2008)
Jack fruit peel Basic blue 9 285.713 mg g1 35400 mg L1 180 min Hameed (2009a)
(Methylene
blue)
Spent tea leaves Basic blue 9 300.052 mg g1 30390 mg L1 180 min Hameed (2009b)
(Methylene
blue)
Sugarcane dust Basic blue 9 3.745 mg g1 12.0 mg L1 30 min 78.02 Khattri and Singh (1999)
Carbonaceous adsorbent Basic blue 9 380 m2 g1 92 mg g1 120 min 6.5 Jain et al. (2003a)
(Methylene 7.5
blue)
Blast furnace (BF) sludge, Basic blue 9 28, 13, 4 m2 g1 6.4, 3.3, 2.1 mg g1 120 min 6.5 Jain et al. (2003a)
BF dust, BF slag (Methylene 7.5
blue)
Diatomite Basic blue 9 27.80 m2 g1 198 mg g1 100400 mg dm3 48 h 11 Al-Ghouti et al. (2003)
(Methylene
blue)
Cedar sawdust, crushed brick Basic blue 9 142.36, 5h Hamdaoui (2006)
(Methylene 96.41 mg g1
blue)
Fly ash (treated with H2SO4) Basic blue 9 6.236 m2 g1 0.0021 mmol g1 2.675  105 72 h Lin et al. (2008)
(Methylene 2.675  104 M
blue)
Fly ash, zeolite, Basic blue 9 15.6, 16.0, 0.02, 0.045 1  1061  10 100, Wang et al. (2005b)
unburned carbon (Methylene 224 m2 g1 0.25 mmol g1 5
M 400 h
blue)
PET carbon Basic blue 9 33.4 mg g1 2h Zhang and Itoh (2003)
(Methylene
blue)
Hazelnut shell Basic blue 9 76.9 mg g1 501000, 50 60 Ferrero (2007)
500 mg L1 180 min
1
Saw dust-walnut Basic blue 9 59.17 mg g 501000, 50 60 Ferrero (2007)
500 mg L1 180 min
Saw dust-cherry Basic blue 9 39.84 mg g1 501000, 50 60 Ferrero (2007)
500 mg L1 180 min
Saw dust-oak Basic blue 9 29.94 mg g1 501000, 50 60 Ferrero (2007)
500 mg L1 180 min
1
Saw dust-pitch pine Basic blue 9 27.78 mg g 501000, 50 60 Ferrero (2007)
500 mg L1 180 min
2 1 1
Sunower stalk Basic blue 9 1.2054 m g 205, 317 mg g 1002000, 100 5 days 80 Sun and Xu (1997)
(Methylene 2000 mg L1
blue),
Basic red 9
Beech sawdust untreated Basic blue 9 9.78, 20.2 mg g1 14 days Batzias and Sidiras (2004)
(Methylene
blue),
Red basic 22
Zeolite Basic dye 14.91 mg g1 20200 mg dm3 410 Meshko et al. (2001)
Maxilon days
Goldgelb GL EC
Zeolite Basic dye 55.86 mg g1 50500 mg dm3 410 Meshko et al. (2001)
Maxilon. days
Schwarz FBL-01
Sawdust carbon Basic green 4 74.5 mg g1 50250 mg L1 Garg et al. (2003)
(continued on next page)
2326 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

Table 2 (continued )

Material Adsorbate Surface area of Adsorption Concentration range Contact pH Percentage Source
adsorbent capacity time adsorption
Neem sawdust Basic green 4 3.42 mg g1 12 mg L1 30 min 7.2 71.25 Khattri and Singh (2000)
AC from pine sawdust Basic green 4 1390 m2 g1 370.37 mg g1 502000 mg L1 3h Akmil-Basar et al. (2005)
Oil palm trunk ber Basic green 4 149.35 mg g1 25300 mg L1 120 min Hameed and El-Khaiary
(Malachite (2008)
green)
AC-groundnut shell Basic green 4 1114 m2 g1 222.22 mg g1 30 min Malik et al. (2007)
(Malachite
green)
Waste material from paper Basic green 4 100 mg L1 1h 98.5, 69.3 Mendez et al. (2007)
industry, pine bark (Malachite
green)
Carbonaceous material Basic green 4 629 m2 g1 75.08 mg g1 1  104 68 h w10066 Gupta et al. (1997)
(Malachite 1  103 M
green)
Sugarcane dust Basic green 4 3.999 mg g1 12.0 mg L1 30 min 83.32 Khattri and Singh (1999)
(Malachite
green)
Carbonaceous adsorbent Basic orange 2 380 m2 g1 75 mg g1 120 min 6.5 Jain et al. (2003b)
(Chrysoidine G) 7.5
Blast furnace (BF) sludge, Basic orange 2 28, 13, 4 m2 g1 10.1, 5.4, 120 min 6.5 Jain et al. (2003b)
BF dust, BF slag (Chrysoidine G) 1.9 mg g1 7.5
Tree fern Basic red 13 408 mg g1 24 h 5 Ho et al. (2005)
Activated sludge Basic red 18 285.71 mg g1 300 min 7 Gulnaz et al. (2004)
Activated sludge biomass Basic red 18 133.9 mg g1 6h Chu and Chen (2002a)
Activated clay Basic red 18 (C.I. 157 mg g1 2h 3 Ho et al. (2001)
11085)
Coal Basic red 2 (C.I. 120 mg g1 101000 ppm 6h McKay et al. (1999)
50240)
1
Bark Basic red 2 (C.I. 1119 mg g 101000 ppm 6h McKay et al. (1999)
50240)
1
Rice husk Basic red 2 (C.I. 838 mg g 101000 ppm 6h McKay et al. (1999)
50240)
Cotton waste Basic red 2 (C.I. 875 mg g1 101000 ppm 6h McKay et al. (1999)
50240)
Human Hair Basic red 2 (C.I. 190 mg g1 101000 ppm 6h McKay et al. (1999)
50240)
2 1 1 1
Bentonite Basic red 2 (C.I. 47.73 m g 274 mg g 50450 mg L 60 min Hu et al. (2006a)
50240)
AC-Plum kernel Basic red 22 1162 m2 g1 710 mg g1 4.1 Juang et al. (2002)
Sugar-industry-mud Basic red 22 519 mg g1 502000 mg L1 3 days Magdy and Daifullah (1998)
Kudzu Basic red 22 210 mg g1 501000 mg dm3 21 days Allen et al. (2003)
Bagasse pith raw Basic red 22 75 mg g1 101000 mg dm3 5 days Chen et al. (2001)
Palm-fruit bunch RAW Basic red 22 180 mg g1 50600 mg dm3 7 days Nassar and Magdy (1997)
AC-Bagasse Basic red 22 (C.I. 607 m2 g1 942 mg g1 4.1 Juang et al. (2002)
11055)
Cane pith Basic red 22 (C.I. 606.8 m2 g1 941.7 mg g1 5 days 4.1 Juang et al. (2001)
11055)
AC-Corncob Basic red 22 (C.I. 943 m2 g1 790 mg g1 4.1 Juang et al. (2002)
11055)
1
Activated sludge biomass Basic red 29 113.2 mg g 6h Chu and Chen (2002a)
AC sludge based Basic red 46 253 m2 g1 188 mg g1 30250 mg L1 2h Martin et al. (2003)
Neem sawdust Basic violet 10 2.355 mg g1 12 mg L1 30 min 7.2 49.08 Khattri and Singh (2000)
Fly ash-Slovakia Basic violet 10 3.26 m2 g1 0.0040 mmol g1 0.050.20 mmol L1 72 h Janos et al. (2003)
Fly ash-Czech Republic Basic violet 10 5.47 m2 g1 0.0115 mmol g1 0.050.20 mmol L1 72 h Janos et al. (2003)
Banana peel Basic violet 10 20.623.5 m2 g1 20.6 mg g1 10120 mg L1 24 h Annadurai et al. (2002)
Orange peel Basic violet 10 20.623.5 m2 g1 14.3 mg g1 10120 mg L1 24 h Annadurai et al. (2002)
Coir pith carbonized Basic violet 10 259 m2 g1 2.56 mg g1 10 min Namasivayam et al. (2001a)
(Rhodamine B)
Coir pith (raw) Basic violet 10 203.25 mg g1 120 min Namasivayam et al. (2001a)
(Rhodamine B)
Sugarcane dust Basic violet 10 3.240 mg g1 12.0 mg L1 30 min 67.50 Khattri and Singh (1999)
(Rhodamine B)
Sewage sludge Basic violet 14 70127 mg g1 101000 mg L1 72 h Seredych and Bandosz
(basic fuchsin) (2007)
1 1
Neem sawdust Basic violet 3 3.789 mg g 12 mg L 30 min 7.2 78.94 Khattri and Singh (2000)
Activated sludge biomass Basic violet 3 113.6 mg g1 6h Chu and Chen (2002a)
Carbonaceous adsorbent Basic violet 3 380 m2 g1 161 mg g1 120 min 6.5 Jain et al. (2003b)
(Crystal violet) 7.5
Blast furnace (BF) sludge, Basic violet 3 28, 13, 4 m2 g1 25, 11, 3 mg g1 120 min 6.5 Jain et al. (2003b)
BF dust, BF slag (Crystal violet) 7.5
2 1 1 1
Activated sewage sludge Basic violet 3 390 m g 270.88 mg g 1001000 mg L 20 min Otero et al. (2003b)
(Crystal violet)
2 1 1 1
Pyrolysed sewage sludge Basic violet 3 80 m g 184.68 mg g 1001000 mg L 90 min Otero et al. (2003b)
(Crystal violet)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2327

Table 2 (continued )

Material Adsorbate Surface area of Adsorption Concentration range Contact pH Percentage Source
adsorbent capacity time adsorption
Sugarcane dust Basic violet 3 3.798 mg g1 12.0 mg L1 30 min 79.13 Khattri and Singh (1999)
(Crystal violet)
1 3
Palm-fruit bunch (raw) Basic yellow 21 327 mg g 50600 mg dm 7 days Nassar and Magdy (1997)
Kudzu Basic yellow 21 160 mg g1 501000 mg dm3 21 days Allen et al. (2003)
Activated sludge biomass Basic yellow 24 105.6 mg g1 Chu and Chen (2002b)

AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon.

adsorption capacity of 1111, 434 and 400 mg g1 for reactive yellow, and Spirogyra sp. exhibited maximum dye removal (88 and 85%,
reactive black and reactive red, respectively for activated carbon respectively) with conditions of pH 3, temperature 30  C and
F400 (Chemviron Carbon, UK) having particle size range of 300 8 g L1 (w/v) biomass concentration after 18 h contact time. It has
500 mm, and compared it with a different study by Juang et al. been reported that pretreatment autoclaving or chemical treatment
(1997), who also investigated the removal of reactive red, reactive also increases the biosorption capacity (Fu and Viraraghavan,
yellow and reactive black but at a particle size of 250420 mm, 2001a; Khalaf, 2008).
respectively by chitosan and reported value of 380, 179 and The decolourization of dyes by biomass involves several
87 mg g1 for the dyes. Though the adsorption capacities were ne complex mechanisms such as surface adsorption, ion exchange,
they were comparatively less than activated carbon. Further, in complexation (coordination), complexationchelation and micro-
a different study on reactive dyes Wu et al. (2000) reported the precipitational, however, limited information is available on the
usefulness of chitosan. The authors found that the bead type of interactions (Banks and Parkinson, 1992; Chu and Chen, 2002a,b)
chitosan gives a higher capacity for dye than the ake type (by and more studies are needed to conrm the interactions. Though
a factor of 24), however, depending on the source of shery wastes. biomass and biosorption can be a promising potential alternative to
A comparison of chitosan akes and beads show that beads can conventional processes for the removal of dyes (Aksu, 2005; Fu and
remove 1103 mg g1 while akes can remove 293 mg g1 of reactive Viraraghavan, 2002a,b, 2001b; Kiran et al., 2006; Robinson et al.,
red 222. This is due to the fact that the beads have a greater surface 2001), it has some limitations such as, the sorption process is
area than the akes. Similar to other adsorbents in an effort to generally slow, pH dependent, and the efuent treatment by
increase the efciency of chitosan, Chao et al. (2004) suggested columns is difcult due to the clogging effect.
enzymatic grafting of carboxyl groups onto chitosan, as a means to Cotton is one of the most important and widely used bers by
confer the ability to adsorb basic dyes on beads. Authors found that humans. Cotton found naturally and consisting cellulose exhibits
the presence of new functional groups on the surface of beads excellent physical and chemical properties in terms of stability,
resulted in increase of the surface polarity and the density of sorp- water absorbency and dye removal ability. A study dealing with the
tion sites thereby improving the sorption selectivity for the dye. adsorption of dyes in a continuous system on treated cotton was
Despite its good efciency there are some disadvantages (Crini, performed by Bouzaida and Rammah (2002). The authors found the
2006; Guibal, 2004; Kumar, 2000; Varma et al., 2004) of using adsorption capacities of cotton for acid blue 25, acid yellow 99 and
chitosan like, the adsorption properties depend on the different reactive yellow 23 to be 589, 448 and 302 mg g1, respectively.
sources of chitin, crystallinity, the degree of N-acetylation, molec- Adsorption behaviour of direct dye on cotton in Aerosol-OT (AOT)
ular weight and solution properties, pH, and vary with afnity for reverse micellar system was studied by Sawada and Ueda (2003),
water, percent deacetylation and content of amino group. exhaustion of dye was suggested to be perfect and superior to that
Biomass which is available in large quantities and at low price in aqueous system. In a study to evaluate the performance of cotton
has got an increasing interest in dye wastewater treatment. A waste for dye removal, McKay et al. (1999) found that the cotton
number of studies (Akar et al., 2006, 2008; Bakshi et al., 2006; waste had the potential to adsorb 875 and 277 mg g1 of basic red 2
Banks and Parkinson, 1992; Chu and Chen, 2002a,b; Fu and Virar- and basic blue 9, respectively.
aghavan, 2002a,b, 2000, 2001a; Khalaf, 2008; Low et al., 1995; Among natural materials clays occupy a prominent position
Tunali et al., 2007) has been carried out to investigate the ef- being low cost, available in abundance and having good sorption
ciencies and mechanism of the removal of dyes by various types of properties. There are various types of clays such as ball clay,
biomass, and some review on biosorption (Aksu, 2005) too exists. bentonite, common clay, sepiolite, re clay, fullers earth (attapulgite
Biomass of non-living dried roots of water hyacinth (without any and montmorillonite varieties) and kaolin. World production of
pretreatment) was explored by Low et al. (1995) as an adsorbent for bentonite was approximately 11.7 Mt and fullers earth production
the removal of methylene blue and victoria blue and the authors was estimated to be 5.61 Mt (http://minerals.usgs.gov/minerals/
found that it possessed good adsorptive capacity of 128.9 and pubs/commodity/clays/claysmyb05.pdf (accessed 26.9.07)). Sales
145.4 mg g1, for methylene blue and victoria blue, respectively. reported by producers for absorbent uses were 3.92 Mt in 2005 and
Biomass has a high potential as a sorbent due to its physico- fullers earth (montmorillonite type) accounted for w68% of the clay
chemical characteristics. Fu and Viraraghavan (2002a,b, 2000, used for absorbents, followed by bentonite and a small amount of
2001a) investigated the removal of various dyes like, basic blue 9, kaolin (http://minerals.usgs.gov/minerals/pubs/commodity/clays/
acid blue 29, congo red, and disperse red 1 by biosorption on dead claysmyb05.pdf (accessed 26.9.07)). In recent years, there has been
and pretreated Aspergillus niger (A. niger) fungus. The authors found an increasing interest in utilizing clay minerals such as bentonite,
that A. niger is capable of removing dyes from an aqueous solution kaolinite, diatomite and fullers earth as adsorbents to remove not
and suggested that three major functional groups: carboxyl, amino only inorganic but also organic molecules. The adsorption efciency
and phosphate, and the lipid fraction in the biomass of A. niger play of clays generally result from a net negative charge (McKay et al.,
an important role in the biosorption of these dyes. A. niger was also 1985b) on the structure of minerals. This negative charge gives clay
used by Khalaf (2008) who studied the biosorbent for removal of the capability to adsorb positively charged species.
a reactive dye synazol from its multi component textile wastewater Clay along with other low-cost materials such as bagasse pith
and compared it with Spirogyra sp., a fresh water green algae. The and maize cob, has been used as adsorbent for removal of dyes
results obtained revealed that dried autoclaved biomass of A. niger astrazon blue, maxilon red and telon blue from aqueous solutions
2328 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

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 Adsorption Concentration Contact pH Percentage Source


adsorbent capacity range time adsorption
PAC Chemviron GW Direct black 168 1026 m2 g1 18.7 mg g1 30250 mg L1 2h Martin et al. (2003)
Filtrasorb 400 (Calgon Direct brown 1 (C.I.No. 30110) 7.69 mg g1 400 min Venkata Mohan et al.
Corporation) (2002)
GAC Filtrasorb 400 Direct red 28 (C.I. 22120) 13.80 mg g1 42 h Fu and Viraraghavan
(Calgon Corporation) (2002a)
PAC from Filtrasorb 400 Direct red 28 (C.I. 22120) 16.81 mg g1 42 h Fu and Viraraghavan
(Calgon Corporation) (2002a)
2 1 1 1
PAC Chemviron GW Direct red 89 1026 m g 8.4 mg g 30250 mg L 2h Martin et al. (2003)
CAC Aldrich Reactive red X6BN Sandoz 163 mg g1 251000 mg L1 24 h 7 Oliveira et al. (2007b)
Filtrasorb 400 (Chemviron Remazol Golden Yellow, 1100 m2 g1 1111, 400, 50 21 days Al-Degs et al. (2000)
Carbon UK) Remazol Red, Remazol Black B 434 mg g1 1000 mg dm3
AC sludge based Direct black 168 253 m2 g1 28.9 mg g1 30250 mg L1 2h Martin et al. (2003)
AC-orange peel Direct blue 86 33.78 mg g1 25125 mg L1 180 min 2 Nemr et al. (2009)
Charnes, lignite coal, Direct brown (C.I.No. 30110) 6.4, 4.1, 50 mg L1 60 min Venkata Mohan et al.
bituminous coal 2.04 mg g1 (2002)
Banana pith Direct red 5.92 mg g1 Namasivayam et al.
(1998)
Fe(III)/Cr(III) hydroxide Direct red 12B 5.0 mg g1 Namasivayam and
Sumithra (2005)
Biogas residual slurry Direct red 12B 3.46 mg g1 5.55 Namasivayam and
Yamuna (1995)
Orange peel Direct red 23, Direct red 80 10.72, 15 min 2 Arami et al. (2005)
21.05 mg g1
Coir pith Direct red 28 6.72 mg g1 Namasivayam and
Kavitha (2002)
Rice hull ash Direct red 28 236.4 m2 g1 171 mg g1 Chou et al. (2001)
Red mud Direct red 28 4.05 mg g1 90 min 7.3 Namasivayam and
Arasi (1997)
Dead fungus Aspergillus Direct red 28 14.16 mg g1 42 h 6 Fu and Viraraghavan
niger (2002a)
Banana peel Direct red 28 (Congo red) 20.6 18.2 mg g1 10120 mg L1 24 h Annadurai et al.
23.5 m2 g1 (2002)
Orange peel Direct red 28 (Congo red) 20.6 14.0 mg g1 10120 mg L1 24 h Annadurai et al.
23.5 m2 g1 (2002)
1 1
Activated red mud Direct red 28 (Congo red) 7.08 mg g 1090 mg L 90 min Tor and Cengeloglu
(2006)
1
Chitosan Direct red 28 (congo red) 81.23 mg g 12 h 7 Wang and Wang
(2007)
Sunower stalk Direct red 28 (Congo red), 1.2054 m2 g1 37.78, 501000, 50 5 days 80 Sun and Xu (1997)
Direct blue 26.84 mg g1 1000 mg L1
Crude sewage sludge Direct red 79 5.28 m2 g1 19.6 mg g1 24 h 6.4 Dhaouadi and
MHenni (2008)
2 1 1 1
Mixture almond shells Direct red 80 10.5 m g 22.422 mg g 50150 mg L 6 Doulati Ardejani et al.
(2008)
Soy meal hull Direct red 80, Direct red 81 0.7623 m2 g1 178.57, 50150 mg L1 24 h 2 Arami et al. (2006)
120.48 mg g1
Chitosan bead Direct red 81 2383 mg g1 5 days 4 Chiou et al. (2004)
(chemically
crosslinked)
AC sludge based Direct red 89 253 m2 g1 49.2 mg g1 30250 mg L1 2h Martin et al. (2003)
Powdered activated Direct yellow 12 98 mg g1 24 h Kargi and Ozmihci
sludge (2004)
Palm oil ash Disperse blue, disperse red 49.5, 61.35 mg g1 60 min 2 Hasnain Isa et al.
(2007)
AC from biomass Euphorbia Disperse orange 25 74121 m2 g1 118.93 mg g1 50 7 Gerel et al. (2008)
rigida 125 mg dm3
1
Modied fungal biomass Disperse red 1 (C.I. 11110) 5.59 mg g 13.50 mg L1 4.0 Fu and Viraraghavan
(Aspergillus niger) (2002b)
Modied sepiolite Reactive black 5 50.5 m2 g1 120.5 mg g1 Ozdemir et al. (2004)
Modied zeolite Reactive black 5 11.8 m2 g1 60.5 mg g1 Ozdemir et al. (2004)
Rhizopus arrhizus Reactive black 5 588.2 mg g1 20800 mg L1 24 h Aksu and Tezer (2000)
biomass
Sunower seed shells, Reactive black 5 50 mg L1 210 min 85, 71 Osma et al. (2007)
mandarin peelings
2 1 1 1
High lime y ash Reactive black 5 5.35 m g 7.184 mg g 5100 mg L 60 min 5.64 Eren and Acar (2007)
Biomass chlorella Reactive black B 555.6 mg g1 20800 mg L1 24 h 2 Aksu and Tezer (2005)
vulgaris
Untreated alunite Reactive blue 114 (C.I. 21620) 2.92 mg g1 120 min 2 Ozacar and Sengil
(2003)
2 1 1
Calcined alunite Reactive blue 114 (C.I. 21620) 66 m g 170.7 mg g 120 min 2 Ozacar and Sengil
(2003)
1
Metal hydroxide sludge Reactive Blue 19 275 mg g 24 h 4 Santos et al. (2008)
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2329

Table 3 (continued )

Material Adsorbate Surface area of Adsorption Concentration Contact pH Percentage Source


adsorbent capacity range time adsorption
Biomass Rhizopus Reactive blue 19 90 mg g1 0500 mg L1 OMahony et al. (2002)
arrhizus (C.I. 61200)
1
Activated sludge Reactive blue 2 250 mg g 240 min Aksu (2001)
(C.I. 61211)
Chitosan bead (chemically Reactive blue2, 2498, 2422, 2436, 5 days 34 Chiou et al. (2004)
crosslinked) reactive red2, 1911 mg g1
reactive yellow2,
reactive yellow86
Charred dolomite Reactive dye Levax 36 m2 g1 950 mg g1 100 14 days Walker et al. (2003)
Brilliant Red E-4BA 2000 mg L1
Squid pens Reactive green 12, 8.82 m2 g1 39.8, 4.83 mg g1 15 days - Figueiredo et al.
Direct green 26 (2000)
Sepia pens Reactive green 12, 4.11 m2 g1 3.46, 56.0 mg g1 15 days Figueiredo et al.
Direct green 26 (2000)
2 1 1
Anodonta shell Reactive green 12, 1.42 m g 0.436, 11.3 mg g 15 days Figueiredo et al.
Direct green 26 (2000)
1 1
Biomass rhizopus arrhizus Reactive orange 16 190 mg g 0500 mg L OMahony et al. (2002)
(C.I. 17757)
Metal hydroxide sludge Reactive red 120 48.31 mg g1 10200 mg L1 7  0.3 Netpradit et al. (2003)
Untreated alunite Reactive red 124 2.85 mg g1 120 min 10 Ozacar and Sengil
(C.I. 17780) (2003)
Calcined alunite Reactive red 124 66 m2 g1 153 mg g1 120 min 10 Ozacar and Sengil
(C.I. 17780) (2003)
1 1
Metal hydroxide sludge Reactive red 141 56.18 mg g 10200 mg L 7  0.3 Netpradit et al. (2003)
Crosslinked chitosan bead Reactive red 189 1936 mg g1 5 days 3 Chiou and Li (2002)
Non-crosslinked chitosan Reactive red 189 1189 mg g1 5 days 6 Chiou and Li (2002)
bead
Metal hydroxide sludge Reactive red 2 62.50 mg g1 10200 mg L1 7  0.3 Netpradit et al. (2003)
Chitosan bead (crab) Reactive red 222 1106 mg g1 3 days Wu et al. (2000)
Chitosan bead (lobster) Reactive red 222 1037 mg g1 3 days Wu et al. (2000)
Chitosan bead (shrimp) Reactive red 222 1026 mg g1 3 days Wu et al. (2000)
Chitosan ake (shrimp) Reactive red 222 494 mg g1 3 days Wu et al. (2000)
Chitosan ake (crab) Reactive red 222 293 mg g1 3 days Wu et al. (2000)
Modied sepiolite Reactive red 239 50.5 m2 g1 108.8 mg g1 Ozdemir et al. (2004)
Modied zeolite Reactive red 239 11.8 m2 g1 111.1 mg g1 Ozdemir et al. (2004)
Biomass rhizopus arrhizus Reactive red 4 (C.I. 18105) 150 mg g1 0500 mg L1 OMahony et al. (2002)
Chromium containing Reactive red X6BN Sandoz 48 mg g1 251000 mg L1 24 h 7 Oliveira et al. (2007b)
leather waste
Modied sepiolite Reactive yellow 176 50.5 m2 g1 169.1 mg g1 Ozdemir et al. (2004)
Modied zeolite Reactive yellow 176 11.8 m2 g1 88.5 mg g1 Ozdemir et al. (2004)
Activated sludge Reactive yellow 2 333.3 mg g1 240 min Aksu (2001)
(CI 18972)
Treated cotton Reactive yellow 23 302 mg g1 Bouzaida and
Rammah (2002)
1
Untreated alunite Reactive yellow 64 5 mg g 120 min 10 Ozacar and Sengil
(C.I. 29025) (2003)
Calcined alunite Reactive yellow 64 66 m2 g1 236 mg g1 120 min 10 Ozacar and Sengil
(C.I. 29025) (2003)
Eucalyptus bark Remazol BB 90 mg g1 500 ppm 2.5 Morais et al. (1999)
Yeast (Saccharomyces Remazol black B 88.5 mg g1 10400 mg L1 Aksu (2003)
cerevisiae)
Yeast (Saccharomyces Remazol blue 84.6 mg g1 10400 mg L1 Aksu (2003)
cerevisiae)
Yeast-C. lipolytica Remazol blue 250 mg g1 100400 mg L1 96 h 2 Aksu and Donmez
(2003)
Yeast-C. tropicalis Remazol blue 182 mg g1 100400 mg L1 96 h 2 Aksu and Donmez
(2003)
1 1
Yeast-Candida sp. Remazol blue 167 mg g 100400 mg L 96 h 2 Aksu and Donmez
(2003)
Yeast-C. quilliermendii Remazol blue 154 mg g1 100400 mg L1 96 h 2 Aksu and Donmez
(2003)
Yeast-C. utilis Remazol blue 114 mg g1 100400 mg L1 96 h 2 Aksu and Donmez
(2003)
1 1
Biomass chlorella Remazol Golden 71.9 mg g 10200 mg L 24 h 2 Aksu and Tezer (2005)
vulgaris Yellow RNL
1 1
Yeast (Saccharomyces Remazol red RB 48.8 mg g 10400 mg L Aksu (2003)
cerevisiae)
Biomass chlorella Remazol red RR 196.1 mg g1 20800 mg L1 24 h 2 Aksu and Tezer (2005)
vulgaris
Crude sewage sludge Vat blue 4 5.28 m2 g1 248.3 mg g1 24 h 9.2 Dhaouadi and
MHenni (2008)

AC activated carbon; GAC granular activated carbon; PAC powdered activated carbon; CAC commercial activated carbon.
2330 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

by Nassar and Elgeundi (1991). Besides determining the adsorption removing hydrophobic contaminants from water. The authors
capacity for each dyeadsorbent system authors determined the compared the results with Na-bentonite and results showed that
relative costs of dye removal. The authors found the relative cost of Na-bentonite and DTMA-bentonite prepared from low-cost natural
the removal of astrazon blue using natural clay, bagasse pith and material have suitable adsorption capacity for the removal of acid
maize cob to be only 1.7%, 3.9% and 4.1% that of carbon, respectively. blue 193 (AB193) from aqueous solution. However, DTMA-
The relative cost of the removal of maxilon red using natural clay, bentonite showed a higher adsorption capacity toward AB193 than
maize cob and bagasse pith was found to be only 2.4%, 8.3% and Na-bentonite. The adsorption capacity of DTMA-bentonite
10.3% that of carbon, respectively. The relative cost of the removal of (740.5 mg g1) was found to be around 11 times higher than that of
telon blue using maize cob, natural clay and bagasse pith was found Na-bentonite (67.1 mg g1) at 20  C. Acid blue 193 has also been
to be only 2.9%, 3.0% and 5.2% that of carbon, respectively. These removed efciently by Ozcan et al. (2005) by modifying bentonite
results showed that clay is the cheapest among the materials used. using surfactant benzyltrimethylammonium (BTMA) chloride.
In a study (McKay et al., 1985b) adsorption capacity of fullers earth Ozcan et al. (2007) also used the surfactant-modied bentonite
for basic and acid blue was reported to be 220 and 120 mg g1, (DTMA-bentonite) for the removal of reactive blue 19 from aqueous
respectively and authors proposed the adsorbent for the treatment solutions. The batch adsorption capacity was found to be
of textile efuents. Al-Ghouti et al. (2003) investigated the removal 206.58 mg g1 for DTMA-bentonite in acidic solutions (pH around
of the problematic reactive dyes as well as basic dyes from textile 1.5), which was suggested to be due to the strong electrostatic
wastewater by diatomite. The adsorption of dye onto diatomite was interactions between its adsorption site and dye anion. The process
suggested to be dependent on electrostatic interactions (depending was found to obey Langmuir model.
on the pH used). The authors suggested that the adsorption Modied sepiolite has been tested as an adsorbent by Ozdemir
capacity increases with increase in pH in the case of cationic dyes, et al. (2004) for azo-reactive dyes. Authors found that the adsorp-
while an opposite effect was observed for anionic dyes. tion capacities can be improved upon modifying their surfaces with
Further, in a study to compare the adsorption capacity of clays quaternary amines. Clay (montmorillonite) coupled with chitosan
with activated carbon, Espantaleon et al. (2003) studied the thereby forming biopolymer chitosan/montmorillonite nano-
removal of the anionic dyes acid yellow 194, acid blue 349 and acid composites was used by Wang and Wang (2007) to study adsorp-
red 423 on natural bentonite and sepiolite and compared it with tion characteristic of congo red. The authors suggested that
activated carbon. The adsorption on sepiolite (98.6, 99.9, compared with chitosan, the nanocomposite had good occulation
95.2 mg g1 for acid yellow 194, acid blue 349, acid red 423, ability in aqueous solution, with comparative low cost (thereby
respectively) was found to be higher than on activated carbon (49.2, overcoming the high cost of chitosan) and relatively high adsorp-
68.2, 26.3 mg g1) but comparable to that on natural bentonite tion capacity in comparison to pure montmorillonite, which was in
(24.9 92.729.1 mg g1). High adsorptive capacity (300 mg g1) for the order 81.23, 12.70, 54.52 mg g1 for chitosan, chitosan/mont-
the removal of dyes (methylene blue) by clay has been observed by morillonite nanocomposites and montmorillonite, respectively.
other workers too (Bagane and Guiza, 2000). Sepiolite was also Besides these various other natural materials such as zeolites
used by Alkan et al. (2007) who studied the adsorption kinetics and (Armagan et al., 2003b, 2004a,b; Benkli et al., 2005; Karcher et al.,
thermodynamics of reactive blue 221(anionic dye), onto sepiolite in 2001; Ozdemir et al., 2004), pumice powder (Akbal, 2005), starch
aqueous solution by batch method. The experimental results by (Crini, 2005; Delval et al., 2003) which is also one of the most
workers showed that the acidic pH, increasing initial dye concen- abundant biopolymers, have also been studied for the removal of
tration and temperature favours the adsorption. Adsorption kinetic dyes. Zeolites (Dabrowski, 2001) are the only existing crystalline
was suggested to follow pseudo-second-order kinetic model con- materials with a well dened pore structure in the microporous
rming the chemisorption of dye onto sepiolite. Authors suggested range. Zeolites used for the removal of dyes have some similarities
that sepiolite could be employed as a low-cost material for the to clays, as the adsorption properties of zeolites also result mainly
removal of textile dyes from efuents. Studies show that the from their ion-exchange capabilities. Nevertheless, the sorption
adsorption capabilities of clays are due to a net negative charge on mechanism of zeolite particles is complex owing to several reasons
the silicate minerals which is neutralized by the adsorption of like their porous structure and surface charges. It is also worth to
positively charged cations such as cationic dyes, heavy metals, etc. mention that the removal efciency of zeolites for dyes may not be
The other main reason for the high adsorption capacity (Cadena as good as that of clay materials, like raw clinoptilolite was not
et al., 1990) of clays is the large surface areas ranging up to found suitable for the removal of reactive dyes due to extremely
800 m2 g1, though pH and temperature also play important roles low sorption capacities (Armagan et al., 2003b, 2004a; Karcher
in determining adsorption capacities. Besides these, various other et al., 2001), similar conclusions have been found by other workers
studies (Armagan et al., 2003a; Harris et al., 2001; Ogawa et al., too (Benkli et al., 2005; Ozdemir et al., 2004). However, the easy
1996; Ozcan et al., 2006a,b; Ozcan and Ozcan, 2005; Ozcan et al., availability and low cost of some may compensate to some extent
2004b; Rytwo et al., 2002; Wang et al., 2004) on the adsorption of for the associated drawbacks. Similar to other adsorbents, some
dyes by kaolinite, montmorillonite, smectites, bentonite are also modications (Armagan et al., 2003b, 2004b) like chemical modi-
available. cation with quaternary amines can be helpful in increasing the
Clays can be modied too to improve their sorption capacity by sorption capacity.
giving some treatments like replacing cations present in clay Industrial/agricultural/domestic wastes or by-products: In
(Cadena et al., 1990), heat treatment (Pradas et al., 1994), acid addition to the above discussed natural materials, a number of
treatment (Espantaleon et al., 2003; Ozcan and Ozcan, 2004). In agricultural wastes/by-products has also been investigated as
a work on bentonite Ozcan et al. (2004a) suggested that the surface adsorbents for the removal of pollutants by a number of workers.
of natural bentonite do not make it a more effective adsorbent for Shells of almond and hazelnut, and poplar and walnut sawdust
the removal of hydrophobic organic compounds from aqueous were investigated by Aydin et al. (2004) for the removal of acid
solution due to the electrically charged and hydrophilic character- green 25 and acid red 183 from aqueous solution. Equilibrium
istics of the surface. They suggested that natural bentonite may be isotherms were determined and analysed using the Freundlich
modied with large organic cations to produce a Dodecyl- equation. Capacities of adsorbent were found to be in the order:
trimethylammonium bromide-modied bentonite (DTMA- walnut > poplar > almond > hazelnut for acid green 25; and
bentonite) in a manner that signicantly improves its capability of almond > walnut > poplar > hazelnut for acid red 183, respectively.
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2331

In order to explore the potential use of ground hazelnut shells and this study too the process was found to obey Langmuir model
sawdust of four wood species, namely walnut, cherry, oak and pitch (better than the Freundlich) and acidic pH favoured the adsorption
pine materials as low-cost adsorbents for methylene blue and acid of both dyes on the adsorbent, however, unlikely to that study here
blue 25 dye removal from dye house efuents, batch and column the adsorption kinetics and the rates of sorption of both dyes were
adsorption studies were carried out by Ferrero (2007). The found to conform to pseudo-second-order model. A numerical
adsorption kinetics with all adsorbents was found to t a second- nite element model to simulate the removal of dissolved textile
order rate equation better than Lagergrens rst-order model. synthetic dyes from wastewater by orange peel taking into
Further, the equilibrium data agreed well with Langmuirs model consideration both the linear and the Langmuir isotherms to
and higher adsorption capacity (given for mean particle diameter describe adsorption process has been proposed (Ardejani et al.,
125 mm in Tables 1 and 2) was observed for hazelnut shells in 2007). The modelling results were compared to those results
comparison to wood sawdust, for both dyes. For methylene blue, obtained from experimental tests for the removal of direct red 23
author observed the adsorption capacity to be even higher (due to and direct red 80 dyes from textile wastewater using orange peel
the presence of polar functional groups) than that for activated adsorbent. The model predictions somewhat agree with the
carbon from the same material which was suggested to be due to experimental measurements.
the fact that thermal activation develops a highly microporous Batzias and Sidiras (2004) studied that beech saw dust as low-
structure, which are unaccessible to large dye molecules and cost adsorbent for the removal of methylene blue and basic red
conversely destroys the functional groups on the surface which are 22. Further, in order to know the effect of chemical treatment and
involved in the adsorption mechanism. to improve its efciency the authors also tested the potential of
El-Geundi (1991) studied maize cob, an agricultural waste, the adsorbent by treating it with CaCl2 (Batzias and Sidiras, 2004)
without any pretreatment for the removal of two basic dyes; and using mild acid hydrolysis (Batzias and Sidiras, 2007a) and
astrazone blue and maxilon red, and two acid dyes; telon blue and found it to increase the adsorption capacity. Besides this, the
erinoyl red. The agricultural waste was found to have high simulation studies for effect of pH were also carried out by Batzias
adsorption capacities of 160 and 94.5 mg g1 for astrozone blue and and Sidiras (2007b). The authors determined the point of zero
maxilon red and low capacities of 47.7 and 41.4 mg g1 for erinoyl charge p.z.c. (5.2) of the sawdust and suggested that increase of
red and telon blue, respectively. Sunower stalks were studied as the pH enhances the adsorption behaviour. The low adsorption of
adsorbents (Sun and Xu, 1997) for basic and direct dyes in aqueous methylene blue at acidic pH was suggested to be due to the
solutions with equilibrium isotherms and kinetic adsorptions. High presence of excess H ions that compete with the dye cation for
adsorption capacities (Table 2) for basic dyes were observed, adsorption sites. With the increase of the pH of the system, the
compared to direct dyes (Table 3) and authors suggested that since number of positively charged sites decreases while the number of
sunower stalks consist of cellulose it is the polyol structure of the negatively charged sites increases. It was also suggested that
cellulose-based materials that has relatively strong chemical the negatively charged sites favour the adsorption of dye (cationic
adsorption of cations such as metal ions and organic bases as well like methylene blue) due to electrostatic attraction. Namasivayam
as physical adsorption of other materials such as acidic and anionic et al. (2001b), investigated coir pith, an agricultural residue, as an
compounds. The coulombic forces between dye species and nega- adsorbent for the adsorption of rhodamine B and acid violet dyes.
tively charged cellulose in water are the major interactions which The source material was used after drying, sieving and carbon-
affect the adsorption of dyes on the materials. Shi et al. (1999) izing at 700  C. It was found that rhodamine B adsorption reached
improved the adsorption capacity of sunower stalks by chemically equilibrium stage at 5, 7, 10, and 10 min for dye concentration 10,
grafting quaternary ammonium groups on them. The modied 20, 30 and 40 mg L1, respectively while crystal violet was found
sunower stalks exhibited increased adsorption capacity for to have equilibration time of 40 min for all concentrations
anionic dyes due to the existence of quaternary ammonium ions on studied. Though this material is freely available the low adsorp-
the surface of the residues. The maximum adsorption capacities on tion capacities viz. 2.56 mg and 8.06 mg g1 of the adsorbent for
modied sunower stalks were found to be 191.0 and 216.0 mg g1 rhodamine B and acid violet, respectively make it poor adsorbent
for congo red and direct blue, respectively, which were at least four for the removal of dyes.
times higher than that observed on unmodied sunower stalks. Lignin a waste/by-product discharged from paper mills in large
Further, they observed that adsorption rates of two direct dyestuffs quantities has been used in its raw state as well as modied state
are much higher on the modied residues than on unmodied for removal of contaminants by researchers. A spherical sulfonic
ones. lignin adsorbent was prepared by Liu and Huang (2006) from
Orange peel waste was studied by Namasivayam et al. (1996) for a bamboo pulp mill by-product. The adsorbent was investigated
the adsorption of congo red, procion orange and rhodamine B dyes. for the removal and recovery of cationic dyes cationic red GTL,
The process was studied at different concentrations of dyes, cationic turquoise GB, and cationic yellow X-5GL, from aqueous
adsorbent dosage, agitation time and pH and was found to obey solutions. Authors found the adsorption to be initial concentration
both the Langmuir and the Freundlich isotherms. Also, the authors and temperature dependent, following both the Freundlich and
suggested that acidic pH is favourable for the adsorption for all the Langmuir isotherms. The process was found to be endo-
three dyes. Orange peel, has also been investigated as an adsorbent thermic, and appreciable Langmuir adsorption capacities of 576.0,
by Sivaraj et al. (2001), for the removal of an acid dye: acid violet 17. 582.4 and 640.8 mg g1 were observed for cationic red GTL,
The material is a waste product with practically no cost but its cationic turquoise GB, and cationic yellow X-5GL, respectively.
adsorption capacity of 19.88 mg g1 makes it an adsorbent of a little Various other studies (Liu et al., 2005; Nikiforov, 1985) on dye
importance for dyes removal from wastewater. Orange peel as LCA removal, and review (Suhas et al., 2007) highlighting the utiliza-
has also been studied by Arami et al. (2005) for the removal of tion of lignin are also available.
direct dyes: direct red 23 and direct red 80. The authors investi- Corncob waste has been investigated as adsorbent for dyes
gated the effects of initial dye concentration (50, 75, 100, (Juang et al., 2002; Wu et al., 2001b). Activated carbons having
125 mg L1), pH, mixing rate, contact time, and quantity of orange surface area in the range of 538943 m2 g1 as prepared from
peel at 25  C. The adsorption capacity was found to be 10.72 and corncob (Juang et al., 2002) were able to remove 2301060 and
21.05 mg g1 at initial pH 2, for direct red 23 and direct red 80, 432790 mg g1 of acid blue 25 (astrazon red) and basic red 22
respectively. Similar to the study of Namasivayam et al. (1996) in (telon blue), respectively. Compared to AC prepared from bagasse
2332 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

(surface area 607 m2 g1) and plum kernel (surface area Besides utilizing natural materials and/or materials obtained as
1162 m2 g1) the removal capacity of AC from corncob for acid blue agricultural wastes as alternative adsorbents for the colour removal
25 was the highest. a number of wastes/by-products which are generated by many
Sawdust (Shukla et al., 2002) is one of the most appealing industries, such as thermal power plants, steel and metal, sugar and
materials among agricultural waste materials, used for removing fertilizer industries etc. have also been used.
pollutants, such as, dyes, salts and heavy metals from water and Fly ash a waste/by-product material is produced in huge amount
wastewater. The material consists of lignin, cellulose and hemi- by coal based thermal power plants. The y ash is generally avail-
cellulose, with polyphenolic groups playing important role for able free of cost and may be used in construction of roads, bricks
binding dyes through different mechanisms. Generally the and cement etc. Owing to its high availability and problem of
adsorption takes place by complexation, ion exchange and disposal, a number of workers have attempted to use it as an
hydrogen bonding. Various fruitful studies have been done on the adsorbent in pollution control. Viraraghavan and Ramakrishna
removal of dyes by sawdust (Garg et al., 2004a; Ho and McKay, (1999) utilized y ash to remove both, cationic and anionic dyes.
1998a; Ozacar and Sengil, 2005), and some adsorption capacities They reported that the dye adsorption process on y ash is of rst
are reported in Tables 1 and 2. Sawdust (from Indian rosewood) order and the adsorption data follow both Langmuir and Freundlich
easily available at zero or negligible price in India (Garg et al., isotherms.
2004a) was studied for the removal of methylene blue. Authors Fly ash as low-cost adsorbent has been investigated by Mohan
studied the effects of different system variables, like adsorbent et al. (2002) for the removal of cationic dyes crystal violet (basic
dosage, initial dye concentration, pH and contact time, and found violet) and rosaniline hydrochloride (basic fuschin). Authors noted
that as the amount of the adsorbent increased, the percentage of that adsorption of dyes increases with increasing temperature,
dye removal increased accordingly. Low concentrations of methy- thereby indicating the process to be endothermic in nature. The
lene blue favoured higher adsorption percentages, and optimum removal of dye was found to be inversely proportional to the size of
pH value for dye adsorption was found to be 7.0. In a study on the the y ash particles. The results obtained by the workers indicated
removal of acid and basic dyes by sawdust, Ho and McKay (1998a) that the Freundlich adsorption isotherm t the data better than the
reported the sorption capacity of basic dye (basic blue 69) to be Langmuir adsorption isotherm. The adsorption of crystal violet and
much higher than acid dye (acid blue 25), which they suggested to rosaniline hydrochloride follow rst-order rate kinetics. Compared
be due to the ionic charges on the dyes and the character of the to the efciency of some other low-cost adsorbents for removal of
biomaterials, also the sorption of dyes was found to be exothermic cationic dyes, the sorption capacity of the y ash for removal of
in nature. Similar to other materials the adsorption capacity of crystal violet (9.76  105 mol g1) and rosaniline hydrochloride
sawdust can also be improved using chemical treatment (Batzias (1.35  105 mol g1) was suggested to be higher.
and Sidiras, 2004; Garg et al., 2003, 2004a,b, 2005). A hard wood Wang et al. (2005a) also used y ash as adsorbent for the
(Mansonia wood) sawdust was studied by Ofomaja and Ho (2008) removal of basic dye, methylene blue, from aqueous solutions and
to know the effect of temperature on the equilibrium biosorption of the adsorption capacity for raw y ash was reported to be
methyl violet dye from aqueous solution onto the material. The 1.4  105 mol g1. The effect of physical (heat) and chemical
equilibrium biosorption data was analysed using Langmuir, treatment was also studied on as-received y ash and the heat
Freundlich and RedlichPeterson isotherms. Best ts were yielded treatment was reported to have adverse effect on the adsorption
with Langmuir and RedlichPeterson isotherms. The process was capacity of y ash but acid treatment (by nitric acid) resulted in an
found to be endothermic in nature and the biosorption was increase of adsorption capacity of y ash (2.4  105 mol g1).
strongly dependent on solution pH and percentage dye removal Similar to the ndings of Mohan et al. (2002) the adsorption
became signicant above pH 7, which was slightly higher than the process here in this case of basic dye was also found to be endo-
pHPZC of the sawdust material. The dependency of dye sorption on thermic in nature. Calcium-rich y ash was studied by Acemioglu
sawdust has also been noted by other workers too (Garg et al., (2004) for the adsorption of congo red from solution with different
2004b; Khattri and Singh, 2000). More about the role of sawdust for contact times, concentrations, temperatures, and pHs. The
the removal of unwanted materials from waters can be found in adsorption was found to be in the range 9398% under the condi-
a review by Shukla et al. (2002). tions studied. Author reported that the adsorption process obeyed
Rice husk as obtained from a local rice mill grounded, sieved, the pseudo-second-order kinetic model and the adsorption
washed and then dried at 80  C was used by McKay et al. (1999) for isotherm followed Freundlich and Dubinin Radushkevich models.
removal of two basic dyes safranine and methylene blue and Similar to other workers ndings in this case also the adsorption
adsorption capacity of 838 and 312 mg g1 was found. Since was found to be endothermic in nature.
disposal or regeneration of spent adsorbent is one of the important Mixtures of y ash-y ash and y ash with other materials have
economic factors in assessing the feasibility of an adsorption also been investigated by various workers (Gupta et al., 1990; Janos
system, authors suggested that as the purchase costs of material is et al., 2003). Gupta et al. (1990) used y ash and coal mixtures for
negligible and it is primarily carbonaceous and cellulosic, the omega chrome red ME dye removal from aqueous solutions. Even
preferred disposal method is by dewatering, drying and burning. for these mixtures the adsorptive capacities were found to be on
Also it was suggested that the heat of combustion can be recovered the lower side. Two y ashes from different power plants fuelled
as waste heat and used for adsorbent drying and steam generation. with different brown coals were tested as potential low-cost
Wool carbonizing waste obtained as a result of processing of wool, sorbents for the removal of synthetic dyes (basic as well as acid)
was investigated by Perineau et al. (1983) for the adsorption of from water by Janos et al. (2003). The adsorption capacities were
dyes. They reported that the surface properties of the material are determined from the parameters of adsorption isotherms and were
such that they tend to adsorb solutes of ionic nature. The authors found to be in the range of 101103 mmol g1 and did not differ
observed that the adsorption of basic dyes is 610 times higher signicantly for basic and acid dyes. However, the authors found
than that of acid dyes. Wheat husk, an agricultural by-product, was that the sorption of basic dyes increased at high pH values, whereas
investigated by Gupta et al. (2007c) as an adsorbent for the the opposite was found for acid dyes. The adsorption was described
adsorption of reactox golden yellow 3 RFN from aqueous solution. well by the multi-site Langmuir isotherm. The dye sorption
The authors suggested that adsorption process can be considered decreased in the presence of organic solvents (methanol, acetone),
suitable for removing colour, COD from wastewater. whereas, inorganic salts exhibited only a minor effect on the dye
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2333

sorption. The presence of oppositely charged surfactants showed after the combustion of shale oil was used as adsorbent by Al-
a pronounced effect on the dye sorption, low concentrations of the Qodah (2000) for dyes. The author reported that the material which
surfactant enhanced sorption, whereas, high concentrations solu- is obtained after a high temperature process possesses good
bilized the dyes and kept them in solution. The authors suggested porosity and suggested that it can have good adsorptive behaviour
that the coal y ashes can be used for the sorption of both basic as for both organic and inorganic pollutants. A two resistance mass
well as acid dyes from aqueous solutions without any expensive transfer model based on the lm resistance and homogeneous solid
pretreatment. Some more interesting features of the utilization of phase diffusion was also developed.
y ash can also be found in review by Wang and Wu (2006). Red mud a by-product of aluminium industry obtained from
By-products/wastes of steel plants viz. blast furnace sludge, bauxite processing by Bayer process has been investigated for
blast furnace dust and blast furnace slag were investigated for the the removal of dyes. Namasivayam and Arasi (1997) studied the
removal of acid (ethyl orange, metanil yellow, acid blue 113) and adsorption of congo red from aqueous solution and suggested the
basic dyes (chrysoidine G, crystal violet, meldola blue, methylene process to be economical since the material is discarded waste.
blue) by Jain et al. (2003a,b,c), the adsorption capacities are given in The removal capacity of the red mud for the dye was 4.05 mg g1.
Tables 1 and 2. The authors compared the materials with a fertilizer The process was found to follow rst rate expression and the
industry waste and standard activated carbon. The adsorption of adsorption data obeyed both Langmuir and Freundlich isotherms.
dyes was reported to follow Langmuir adsorption model and was Authors noted the mechanism of adsorption to be mostly ion
rst order in nature. Authors observed that compared to standard exchange. Red mud has also been used by Wang et al. (2005a) who
activated charcoal the removal capacities were less. Slag as an investigated it for the removal of basic dye, methylene blue, from
adsorbent for removal of various other dyes has been investigated aqueous solutions and found the adsorption capacity for raw red
by other workers too (Gupta et al., 2003, 1997; Li et al., 2003; mud as 7.8  106 mol g1. The effect of physical (heat) and chem-
Ramakrishna and Viraraghavan, 1997). A sludge obtained by ical treatment was also studied on as-received red mud and was
precipitation of metal ions in wastewater with calcium hydroxide reported to have adverse effect on the adsorption capacity. The acid
in electroplating industry has been investigated for the removal of treatment (by nitric acid) resulted in a decrease of adsorption
dyes (azo) by Netpradit et al. (2003, 2004a,b). The authors noted capacity of red mud (3.2  106 mol g1). Some other fruitful
a maximum adsorption capacity (4862 mg g1) for azo-reactive studies (Gupta et al., 2004b; Tor and Cengeloglu, 2006) have also
(anionic) dyes and suggested that metal hydroxide sludge being been carried out on adsorption of various dyes such as rhodamine
a positively charged adsorbent can remove azo-reactive (anionic) B, fast green, methylene blue and congo red on red mud.
dyes and the charge of the dyes is an important factor for the Aerobically digested sludge (Martin et al., 2003) from an urban
adsorption due to the ion-exchange mechanism. wastewater was tested for producing activated carbons and
McKay et al. (1987) studied bagasse pith from the sugarcane further used for dye removal in order to overcome the costs of
industry without any pretreatment for the removal of two basic ACs in water treatment. The sludge based (SB) AC was mainly
dyes, basic blue 69 and basic red 22, and two acidic dyes, acid blue mesoporous in nature, with a surface area of 253 m2 g1 and an
25 and acid red 114, from aqueous solutions. High adsorptive average pore diameter of 2.3 nm. The ACs so produced were used
capacity was observed for the adsorption of the basic dyes, for the removal of three anionic dyes viz. acid brown 283, direct
158 mg g1 for basic blue 69 and 77 mg g1 for basic red 22, while red 89 and direct black 168 and a basic dye basic red 46 from
lower capacities of 23 mg g1 and 22 mg g1 were observed for acid aqueous solutions. The SBAC was found to perform nearly as well
red 114 and acid blue 25, respectively. The same material was also as Chemviron, AC which was mainly microporous with a surface
used by Al-Duri et al. (1990) for developing a mass transfer model, area of 1026 m2 g1 and an average diameter of 1.8 nm. The
based on external mass transport, macropore and micropore greater capacity of AC sludge based (Tables 1 and 3) compared
diffusion to predict concentration versus time decay plots of with the commercial AC to remove acid and a direct dye from
adsorption. Gupta et al. (2000) used bagasse y ash for the removal solution is attributed to its wider pore size distribution. The
of two important basic dyes, rhodamine B and methylene blue. The authors also reported that the presence of acidic surface func-
source material was treated with hydrogen peroxide and then tional groups in SBAC also plays an important role in determining
washed, dried and further sieved into desired particle sizes. The the extent of adsorption as a function of solution pH. Sewage
authors estimated the cost of nished adsorbent as 12 US $ per ton, sludge has also been used to prepare carbonaceous materials
which was quite cheap. using chemical activation by Rio et al. (2005). Carbonaceous
Rice husk ash (Sumanjit and Prasad, 2001) a waste from rice sorbents so developed from sludge were used to remove copper
mills has been used as an adsorbent for removal of acidic dyes ion, phenol and dyes (acid red 18 and basic violet 4) from aqueous
namely acid violet 54, acid violet 17, acid blue 15, acid violet 49 and solution as well as volatile organic compounds from the gas
acid red 119 and their COD from aqueous solutions. The adsorption phase. Two experimental conditions were suggested by the
capacity was found to vary from 99.4 to 155 mg g1, making rice authors but in order to have a high mass yield and to reduce the
husk ash a good material. Further, a time period of 30120 min was energetic cost of the process, the optimal condition having 1.5 g of
found to be optimum for attaining equilibrium. H2SO4 g1 of sludge, 700  C and 145 min was suggested to be
Hasnain Isa et al. (2007) studied the possibility of using palm oil more appropriate.
ash as a low-cost adsorbent for the removal of the dyes disperse A waste carbon slurry generated during liquid fuel combustion
blue and disperse red from aqueous solution. Both batch as well as in fertilizer plants has been converted into an inexpensive activated
continuous ow experiments were performed, and the effects of carbon by Gupta et al. (1997). Authors prepared an activated carbon
different system variables, including pH, initial dye concentration and fruitfully employed it for a basic dye (malachite green) removal,
and agitation time, were studied in the batch tests. It was suggested a 100% removal was observed at low concentrations. Presence of
that acidic pH favoured dye removal, and the optimum pH and anionic surfactant (Manoxol-1B) was tested and found not to affect
agitation time for the removal of the two dyes were found to be 2 the uptake of dye signicantly. The dye removal was suggested to
and 60 min, respectively. Besides this the authors also suggested take place through a lm diffusion mechanism at lower concen-
that ash can be used in its natural form in batch processes while trations (5  105 M) and by particle diffusion at higher concen-
pelletisation, due to cost implications, is not recommendable for trations (>5  105 M). Authors found that the adsorbent can be
industrial application. Shale oil ash, an inorganic residue, obtained regenerated to quantitatively recover the dye with acetone and the
2334 V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342

developed adsorbent was cheaper than commercially available 2005), pyrite and synthetic iron sulde, alum-impregnated acti-
carbons. A similar carbonaceous adsorbent was investigated by Jain vated alumina, sorels cement, calcined alunite (Tunali et al., 2006),
et al. (2003b,c, 2004) who utilized it for the removal of dyes and rosa canina seeds (Gurses et al., 2006) etc. have also been explored
phenols. The authors compared the efciencies of the carbonaceous as adsorbents.
adsorbent with blast furnace slag, dust and sludge (steel industry
waste) and found the carbonaceous adsorbent to be the best among 5. LCA efciency and cost comparison
them. Further, comparison of the carbonaceous adsorbent with an
activated carbon showed it to be w45% efcient for acid dyes (ethyl Efciency (or adsorption capacity as discussed in the article) of
orange, metanil yellow and acid blue 113) and 7080% efcient for a material is an important aspect as understood by the studies
basic dyes (chrysoidine G, crystal violet, and meldola blue) as reported in preceding paragraphs, but it is (should be) relative as it
compared to a commercial activated carbon. Authors proposed that need to be compared with some standard adsorbent like AC or
the carbonaceous adsorbent being a low-cost material need not be some other one closer to the material under investigation. Besides
regenerated after being loaded with pollutants and can be disposed this, adsorbent cost is an important factor and may be helpful in
of by burning. comparing the materials; however, it is seldom reported in the
Various other materials have also been put to use for preparing research papers. Fig. 3 and Tables 13 present efciencies and cost
alternative adsorbents. An attempt to remove methylene blue and estimates for some of the commercial activated carbons reported
methyl orange by alginate beads containing magnetic nanoparticles along with cost of some adsorbents. According to these bagasse
and activated carbon was made by Rocher et al. (2008), so as to yash, peat, sphagnum moss peat, fullers earth, BF slag, bentonite,
develop a low-cost methodology having low impact on environ- manganese oxide, fullers earth, carbonaceous adsorbent (fertilizer
ment. The adsorption capacity of beads was found to be higher than industry waste) are the materials costing 0.1 US $ per kg making
non-encapsulated AC for methylene blue and was of same order of them useful materials in terms of cost as compared to commercial
magnitude for methyl orange. In a study, Shimada et al. (1999) used ACs which normally costs more than 1.5 US $ per kg. However,
newspaper as raw material for the production of activated carbon. these estimates should be considered as indicative, as the cost as
The raw material mixed with 8% phenol resin resulted in activated well as adsorption capacity may vary (as evident from previous
carbons having good surface area (1000 m2 g1) and yield (40%). In sections and Tables 13). The cost of the precursor and/or the nal
view of its high surface area this product functioned as a good material depends on various factors which include its availability,
adsorbent, as evident by high iodine (1310 mg g1) and methylene whether it is natural, industrial/agricultural/domestic wastes or by-
blue number (326 mg g1). products or synthesized products, the processing required, the
Besides these various other materials such as waste tyre rubber treatment conditions and both recycle and lifetime issues. The cost
(San Miguel et al., 2002), polymer materials (Ravi et al., 2006), will also vary when/where the adsorbents are made, in/for devel-
layered double hydroxides (Bouraada et al., in press, 2008), bottom oped countries, developing countries or underdeveloped countries.
ash (Gupta et al., 2005a, 2006a,b, 2004a), de-oiled soya (Gupta Mainly a combination of these two factors can be helpful in pre-
et al., 2005b, 2006a,b, 2008), black tea leaves, tree fern (Ho et al., dicting the actual applicability of LCAs.

20
18
16
Price (US $/kg)

14
12
10
8
6
4
2
0
BFA

Peat

SM peat

Fullers earth 1

BF slag

Bentonite

Manganese oxide

Fullers earth 2

CAF

CSC

Starch xanthate

Spheroidal cellulose

CAC 1

Perlite

AC(almond shell)

CAC 2

CAC 3

Chitosan

CAC 4

Adsorbents
BFA - Bagasse flyash
SM - Sphagnum moss
CAF - Carbonaceous adsorbent (fertilizer industry waste)
CSC - Coconut shell charcoal (as received)
CAC - Commercial activated carbon

Fig. 3. Cost of adsorbents (low-cost adsorbents & commercial activated carbons) as reported in literature. Source: (Atun et al., 2003; Babel and Kurniawan, 2003, 2004; Chakravarty
et al., 2002; http://minerals.usgs.gov/minerals/pubs/commodity/clays/claysmyb05.pdf (accessed 26.9.07); http://minerals.usgs.gov/minerals/pubs/commodity/peat/peat_myb05.pdf
(accessed 3.10.07); Jain et al., 2003c; Mathialagan and Viraraghavan, 2002; Sharma and Forster, 1993; Srivastava et al., 1997, 1995; Tare et al., 1992; Toles et al., 2000). Water for
People Water for Life United Nations World Water Development Report UNESCO, http://www.unesco.org/water/wwap/wwdr1/pdf/chap9.pdf (accessed on 13.10.07).
V.K. Gupta, Suhas / Journal of Environmental Management 90 (2009) 23132342 2335

6. Combination of methodologies/techniques The literature review shows that there is a need for more
detailed systematic studies on dye removal process and also some
Some workers have used the methods in conjunction with each technical improvements in preparing and utilizing adsorbent. As
other or some other process. A combination of adsorption and regards to future work, the following recommendations are
nanoltration (NF) was adopted for the treatment of a textile dye- suggested.
house efuent containing a mixture of two reactive dyes (Chakra- As discussed in earlier sections there exists a big variety of dyes
borty et al., 2005). The efuent stream was rst treated in a batch and their removal is based on various factors which include
adsorption process with a waste carbonaceous material (sawdust) as adsorbateadsorbent relationships (interactions), size of adsorbate,
an adsorbent to reduce the dye concentration of the efuent by role of functional groups on both adorbate as well as adsorbent,
about 83% for reactive red CNN and 93% for reactive black B. The a more detailed work on these interactions is needed for the studies
efuent from the adsorption unit was passed through an NF unit for to correlate and compare.
the removal of the remaining small amount of dyes and to recover Research in the same laboratory will be preferred in order to
the associated chemicals (mainly salt) in the efuent stream. The compare the adsorptive nature of LCA for different dyes. Also,
authors found that the dyes remaining after this step were less than a report in more depth and details of the materials used, and their
1 ppm. The percentage removal of COD was found to be greater than constituents need to be presented. Since sometimes differences are
99%, and the salt recovery was w90%. Authors also compared the found in adsorption capacities for different adsorbents of the same
performance of the proposed method with that of direct NF of the origin, this indicate that there exists some relationship between
same efuent. The salt recovery and the COD reduction were adsorptive properties and the molecular structure or the surface
reported to be comparable in both methods but the dye concen- groups of the adsorbent, besides the surface area/porosity effect,
trations in the permeate stream were above the permissible limit and needs more detailed critical investigations. This hopefully will
with the direct NF method. The major drawback in direct NF was help in predicting and selecting adsorbents. If the materials are of
suggested to be the substantial reduction in the permeate ux different origins then a critical evaluation of materials with
compared to the combined method. Various other workers have also a comparison of some similar adsorbent materials should be
investigated and reported a combination of technologies like Gra- preferred. Further, detailed systematic studies are needed to nd
ham et al. (1992) tried to remove colour by ltration with coagula- out which component in the precursor is primarily responsible for
tion while Lin and Lin (1993) used ozonation with coagulation. On the development of surface area or micro/meso porosity or is
the other hand Lin and Peng (1996) used coagulation in combination helpful in development of functional groups.
with electrochemical oxidation and activated sludge for treating If possible, pore size distribution of adsorbent, size of dye
textile wastewaters. A combination of methodologies have been molecule/s, functional groups present on surface of adsorbent,
suggested (Forgacs et al., 2004; Rai et al., 2005; Robinson et al., 2001) initial pH, batch or column conditions, temperature, particle size of
and some nice reviews (Hai et al., 2007; van der Zee and Villaverde, adsorbent, the furnace as well as sample holder size (in case acti-
2005; Vandevivere et al., 1998) are also available on it. vation is performed) should be provided. The adsorbent cost (raw
material, nal product at lab scale) may also be made available, so
7. Conclusions and future perspectives that other workers can also compare the materials easily.
Once batch conditions, characterization of adsorbents, adsorp-
The literature reviewed revealed the fact that there has been tive capacity and the uptake mechanism are investigated work
a high increase in production and utilization of dyes in last few should be done to design and carry out some pilot-plant scale
decades resulting in a big threat of pollution. It is worthwhile studies to check their feasibility at industrial level. As the dye
noting that the removal of dyes can be done by various techniques; efuents contain several other pollutants, attention has to be given
however, there exists no such methodology which can successfully to adsorption of dyes from mixtures and the LCAs should further be
remove all types of dyes at low cost. The literature survey results investigated for their efciency using dye efuents from industries.
and the methods discussed above lead us to the conclusion that for Research workers should be encouraged to work on real efuents at
removal of dyes either adsorption alone or a combination of local level. Since a vast number of the low-cost adsorbents are
processes involving adsorption can give fruitful results. However, as produced from locally available materials, the researchers utilizing
noticed the main drawback in adsorption is the high cost of LCA for dye removal can work and promote mantra think globally,
adsorbents as activated carbons are not low-cost materials and act locally. Combination of methodologies/system should also be
hence, in spite of their good efciency and applicability for encouraged since one perfect method/system is practically difcult.
adsorbing a wide variety of materials, their use can sometimes be Besides these, strategies to minimize dye and related chemical
restricted due to economic considerations. Besides this, the efuent at all levels, and designing more environmentally friendly
regeneration is expensive and involve adsorbent loss as well as chemicals are also needed.
efciency. As regulations become stricter, the effectiveness and cost
of treatment processes for dye becomes more signicant. The dye
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