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Advances in Environmental Research 7 (2003) 471–478

Activated carbon from coconut coirpith as metal adsorbent:

adsorption of Cd(II) from aqueous solution
K. Kadirvelu*, C. Namasivayam
Defence Research & Development Organisation (DRDO), Centre for Environment and Explosives Safety (CEES),
Metcalfe House, Delhi 110054, India

Accepted 21 February 2002


Activated carbon prepared from coirpith, an agricultural solid waste by-product, has been used for the adsorption
of Cd(II) from aqueous solution. Parameters such as the agitation time, metal ion concentration, adsorbent dose and
pH were studied. The adsorption data fit well with the Langmuir and Freundlich isotherm models. The adsorption
capacity (Q0) calculated from the Langmuir isotherm was 93.4 mg Cd(II)yg at an initial pH of 5.0 at 30 8C for the
particle size 250–500 mm. The percent removal increased with pH from 2 to 4 and remained constant up to pH 10.
Desorption studies were performed with dilute hydrochloric acid. Quantitative recovery of the metal ion is possible.
The mechanism of adsorption seems to be ion exchange. As coirpith is discarded as waste from coir processing
industries, the carbon is expected to be an economical product for metal ion remediation from water and wastewater.
䊚 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Coirpith carbon; Cd(II) adsorption; Kinetics; Isotherms; pH; Desorption

1. Introduction water and wastewater before its transport and cycling

into the natural environment.
Rapid industrialization has led to increased disposal With better awareness of the problems associated
of heavy metals into the environment. Cadmium is with cadmium came an increase in research studies
introduced into water from smelting (Buchaver, 1973), related to methods of removing cadmium from waste-
metal plating, cadmium nickel batteries, phosphate fer- water, for which a number of technologies have been
tilizers, mining, pigments, stabilizers, alloy industries developed over the years. The most important technol-
and sewage sludge (Kadirvelu, 2000). The harmful ogies include chemical precipitation, electroflotation, ion
effects of cadmium include a number of acute and exchange, reverse osmosis and adsorption onto activated
chronic disorders, such as itai-itai disease, renal damage, carbon (Poon, 1986). These methods are not cost-
emphysema, hypertension and testicular atrophy (Kadir- effective in the Indian context. Low-cost and non-
velu, 2000). In India the tolerance limit for cadmium conventional adsorbents include agricultural wastes,
for discharge into inland surface waters is 2.0 mgyl such as natural compost, Irish peat, planer shell, walnut
(ISI, 1982) and for drinking water is 0.01 mgyl (IS, shell, and biomass, such as Aspergillus tureens and
1991). Hence, it is essential to remove Cd(II) from Macular remanniamus (Azab and Peterson, 1989), chi-
toson (Muzzarelli and Rocchetti, 1986), and peat moss
*Corresponding author. Tel.: q91-422-880716; fax: q91- (Chaney and Hundemann, 1979). Oxidized anthracite
422-422387. (Petrov et al., 1992) silica gel (Filho et al., 1995),
E-mail address: (K. Kadirvelu). bituminous coal (Singh and Rawat, 1994), goethite

1093-0191/03/$ - see front matter 䊚 2002 Elsevier Science Ltd. All rights reserved.
PII: S 1 0 9 3 - 0 1 9 1 Ž 0 2 . 0 0 0 1 8 - 7
472 K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478

Fig. 1. Effect of agitation time and initial Cd(II) concentration on the adsorption of Cd(II). Conditions: initial pH 5.0; carbon
concentration 20 mgy50 ml.

(Johonson, 1990), blast furnace sludge (Degodo et al., of adsorption of Cu(II) and Hg(II) and Pb(II) from
1998), red mud (Apak et al., 1998; Lopez et al., 1998) aqueous solutions using coirpith carbon have recently
wollastonite (Sharma et al., 1990) bentonite (Bareket et been reported (Namasivayam and Kadirvelu, 1997b,
al., 1997) and peat (McKay and Porter, 1997) have also 1999).
been tried for the removal of Cd(II) from water and The objective of this study was to investigate the
wastewater. Activated carbon obtained from peanut hull feasibility of using carbonized coirpith for the removal
(Periasamy and Namasivayam, 1994), almond shell, of Cd(II) from aqueous solution by adsorption.
olive stones and peach stones (Ferro-Gracia et al., 1988)
and commercial activated carbons (Periasamy and 2. Materials and methods
Namasivayam, 1994) have also been used for Cd(II)
removal. Marshall and Johns (1996) have used agricul- 2.1. Adsorbent
tural by-products as adsorbents for removal of metal
ions from aqueous solution. India, the third largest Waste coirpith was collected from coir processing
producer of coconut in the world, produces approxi- industries located in Pollachi, Coimbatore district, Tamil
mately 8160 million coconuts every year. Coirpith Nadu state, India and dried in sunlight. The preparation
constitutes as much as 70% of the husk, and is a light, and characteristics of activated carbon from coirpith
fluffy material generated in the separation of the fiber have already been reported (Namasivayam and Kadir-
from the husk. It is estimated that the production of velu, 1997a,b). All the chemicals used were of analytical
coirpith in India is 0.5 million t. Coirpith is disposed of reagent grade. All the solutions were prepared with
as waste and its accumulation around coir processing double-distilled water.
centers is creating a menace (Kadirvelu, 2000). We
have reported our preliminary findings that carbonized 2.2. Batch-mode adsorption studies
coirpith was effective for the treatment of dyeing indus-
try wastewater and the removal of As, Cu, Cr, Hg, Ni The adsorbate stock solution of 1000 mgyl Cd(II)
and organics, including pesticides from aqueous solution was prepared from cadmium sulfate (CdSO4Ø8H2O) in
(Namasivayam and Kadirvelu, 1994, 1998). Different distilled water containing a few drops of nitric acid to
methods of preparation of activated carbon from coirpith prevent hydrolysis. The stock solution was diluted as
(Namasivayam and Kadirvelu, 1997a), and the kinetics required to obtain standard solutions containing 5–40
K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478 473

Fig. 2. Effect of carbon concentration on adsorption of Cd(II). Conditions: initial pH 5.0; agitation time 1 h.

mgyl Cd(II). Batch-mode adsorption studies were car- 3. Results and discussion
ried out with 20 mg of adsorbent and 50 ml of Cd(II)
solution of desired concentration at an initial pH of 5.0 3.1. Influence of agitation time and initial Cd(II)
wpH range: 5.0 (initial)–6.2 (final)x in 100-ml conical concentration
flasks, which were agitated at 160 rev.ymin for prede-
termined time intervals at room temperature (30 8C) on Fig. 1 shows the effect of agitation time and Cd(II)
a mechanical shaker. At the end of the agitation time concentration on removal. Equilibrium adsorption was
the suspensions were centrifuged at 8600=g. Aliquots established within 40 min for 10 mgyl Cd(II), 50 min
of the supernatant were withdrawn and Cd(II) was for 20 mgyl Cd(II) and 60 min for 30 and 40 mgyl
spectrophotometrically estimated (Hitachi U 3210, Cd(II). It is very clear from the results that the agitation
Tokyo) using pyronine G at a wavelength of 540 nm time required for maximum uptake of metal ions by
(Prasad Rao and Ramakrishna, 1982). The sensitivity carbon was dependent on the initial Cd(II) concentra-
of this method is such that the concentration of Cd(II) tion. This result is interesting because equilibrium time
can be determined to 0.3 mgyl. Adsorption isotherm is one of the parameters for economical wastewater
studies were carried out with eight different initial treatment plant applications. According to these results,
concentrations of Cd(II) from 5 to 40 mgyl while the agitation time was fixed at 2 h for the rest of the
maintaining the adsorbent dosage at 20 mgy50 ml. The batch experiments to make sure that equilibrium was
effect of adsorbent dosage on percent removal was reached. It also shows that increases in metal ion
studied using Cd(II) concentrations of 20 and 40 mgyl. concentration increased the amount of metal ion uptake
Langmuir and Freundlich models were applied to the per unit weight of carbon (mgyg).
adsorption isotherm and different constants were gen-
erated. The effect of pH on Cd(II) removal was studied 3.2. Adsorption kinetics
using a 20-mg carbon dose and Cd(II) concentrations
of 20 and 40 mgyl. Control experiments were also The kinetic study for the adsorption of Cd(II) was
carried out. conducted at optimum pH (5.0) where only adsorption
takes place. The adsorption of Cd(II) was complete in
2.3. Desorption studies 1 h for the concentrations 10–40 mgyl. The adsorption
rate constants (Kad ) were calculated on the data in Fig.
After adsorption experiments with 40 mgyl Cd(II) 1 using Lagergren’s equation (Kadirvelu, 2000):
and 20 mg of carbon, the cadmium-loaded carbon was
log10Žqeyq.slog10qeyŽ (1)
separated and gently washed with distilled water to
remove any unadsorbed Cd(II). It was then agitated where, q is the amount of Cd(II) adsorbed in mgyg at
with 50 ml of hydrochloric acid of various concentra- time t, qe is the amount of Cd(II) adsorbed (mgyg) at
tions (0.025–0.15 M) and the amount of desorbed equilibrium time and Kad is the rate constant of adsorp-
cadmium was estimated. tion (1ymin). Linear plots of log10 (qeyq) vs. t show
All the experiments were carried out in duplicate and the applicability of Eq. (1) for coirpith carbon.
the mean values are presented. The maximum deviation The Kad values calculated from the slope of the linear
was 2.0% (standard deviation was "2%). plots were found to be 11.12, 7.9, 4.58 and
474 K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478

3.3. Effect of carbon dosage

Fig. 2 shows the removal of Cd(II) as a function of

carbon dosage. Increasing carbon dosage increased the
percentage removal of Cd(II). For quantitative removal
of Cd(II) from a 50-ml aliquot of 20 and 40 mgyl
Cd(II), a minimum dose of 20 and 70 mg, respectively,
was required.

3.4. Adsorption isotherms

Fig. 3 shows the adsorption isotherm for Cd(II) on

coirpith carbon. The Langmuir isotherm was applied for
equilibrium adsorption (Langmuir, 1918):
Ceyqes1yQ0bqŽCeyQ0. (2)
where Ce is the equilibrium concentration (mgyl), qe is
the amount adsorbed at equilibrium (mgyg), and Q0
and b are Langmuir constants related to the adsorption
capacity and energy of adsorption, respectively. The
linear plots of Ce yqe vs. Ce show that adsorption follows
the Langmuir isotherm model (Fig. 4). The correlation
coefficient was 0.9996. Q0 and b were determined from
the slope and intercept of the plot and were found to

Fig. 3. Adsorption isotherm of Cd (II).

2.96=10y2 1ymin for initial concentrations of 10, 20,

30 and 40 mgyl, respectively. The Kad values were
comparable with recently reported values for agricultur-
al-based activated carbon: 5.36, 6.03 and 4.48 for initial
concentrations of 10, 15 and 20 mgyl, respectively
(Periasamy and Namasivayam, 1994).
In order to develop design models for wastewater
treatment systems, the mechanism of adsorption should
be known, described by:

1. Mass transfer across the boundary layer surrounding

the adsorbing particle;
2. Mass transfer within the internal surface of the
particle; and
3. Adsorption at the site.

The constant for intraparticle diffusion Kp was cal-

culated from the slope of the linear portion of the plots.
The constants (Kp) were found to be 20.0, 26.8, 32.2 Fig. 4. Langmuir plot for Cd(II) adsorption. Conditions: initial
and 36.6=10y1 mgyg min1y2 for initial Cd(II) concen- pH 5.0; carbon concentration 20 mgy50 ml; Cd(II) concentra-
trations of 10, 20, 30 and 40 mgyl, respectively. tion 10–40 mgyl.
K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478 475

Table 1
Comparison of adsorption capacity for Cd(II) with other adsorbents

Adsorbent Q0 Reference
Fly ash 198.2 Lopez et al., 1998
Fly ash washed with water 195.2 Lopez et al., 1998
Fly ash washed with acid 180.4 Lopez et al., 1998
Carbonized coirpith 93.2 This work
Peanut hull carbon 89.4 Periasamy and Namasivayam, 1994
Red mud washed with water 66.8 Lopez et al., 1998
Red mud acid-treated at 600 8C 66.8 Lopez et al., 1998
Red mud acid-treated 46.9 Lopez et al., 1998
Fe(III)yCr(III) hydroxide 40.5 Namasivayam and Ranganathan, 1995
Modified silica gel 33.72 Filho et al., 1995
Granular activated carbon 11.1 Periasamy and Namasivayam, 1994
Bituminous coal 6.47 Singh and Rawat, 1994
Olive stone carbon 5.91 Ferro-Gracia et al., 1988
Moss 46.6 Low and Lee, 1991
Peach stone carbon 3.27 Ferro-Gracia et al., 1988
Goethite 3.08 Johonson, 1990
Almond-shell carbon 2.7 Ferro-Gracia et al., 1988
Peat 21.13 McKay and Porter, 1997
Furnace sludge 7.39 Degodo et al., 1998
Oxidized anthracite 28.1 Petrov et al., 1992

be 93.4 mgyg and 1.73 lymg, respectively. Values of incorporating all factors affecting the adsorption process,
the adsorption capacity of other adsorbents from the such as adsorption capacity and intensity, respectively.
literature are given in Table 1 for comparison. Kf and n were calculated from the slope of the Freun-
The essential characteristics of the Langmuir isotherm dlich plots. The constants were found to be Kfs27.51
can be expressed in terms of a dimensionless constant and 33.75 and ns2.08 and 3.19 for 20 and 40 mgyl
separation factor or equilibrium parameter, RL , which is Cd(II) concentrations, respectively. Accordingly to
defined as: Kadirvelu and Namasivayam (2000), it has been shown
that n values between 1 and 10 represent beneficial
RLs1yŽ1qbC0. (3) adsorption.
where b is the Langmuir constant and C0 is the initial
concentration of Cd(II). The RL value indicates the 3.5. Effect of pH
shape of the isotherm as follows:
Fig. 5 shows the effect of pH on the removal of
RL value Type of isotherm Cd(II) by coirpith carbon and precipitation. The Cd(II)
RL)1 Unfavorable removal by coirpith carbon increased with increasing
RLs1 Linear pH and attained values of 98 and 85% for 20 and 40
0-RL-1 Favorable mgyl of Cd(II), respectively, at an initial pH of 4.0. It
RLs0 Irreversible is evident that the carbon is effective for the maximum
removal of Cd(II) over the pH range 5–10. The increase
in metal ion removal as pH increases can be explained
According to McKay et al. (1982), RL values between on the basis of a decrease in Hq on the surface sites
0 and 1 indicate favorable adsorption. The RL values and by a decrease in positive surface charge, which
were found to be between 0.0142 and 0.0545 for results in less repulsion of adsorbing metal ions.
concentrations of 10–40 mgyl Cd(II). The efficiency of Cd(II) removal is affected by the
The Freundlich isotherm is represented by the equa- initial metal ion concentration, with decreasing removal
tion (Freundlich, 1906): percentages as concentration increases from 20 to 40
qesKfCe1yn (4) mgyl at constant pH. This effect can be explained as
follows: At low metal ionycarbon ratios, metal ion
where Ce is the equilibrium concentration (mgyl), qe is adsorption involves the higher energy sites. As the metal
the amount adsorbed (mgyg) and Kf and n are constants ionycarbon ratio increases, the higher energy sites are
476 K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478

Seco et al. (1999) for cadmium and copper removal by

granular activated carbon, Kumar and Dara (1980) for
the uptake of copper, lead and cadmium by acacia bark,
and by Periasamy and Namasivayam (1994) for cad-
mium removal by peanut and commercial activated
carbons. The mechanism of adsorption can also be
explained based on ion exchange models. On the acti-
vated carbon surface (S), a carbon–oxygen complex
binds metal ions by displacing protons from the carbon
surface as follows:
2S–COHqMqlS–(CO)2Mqq2Hq (5)
2q 2q
qM lS–COM q2H q
The above mechanism is suggested to occur in the
present case because, at increasing initial metal-ion
concentrations, the final pH of the solution decreases.
This suggests that greater adsorption of Cd(II) releases
Fig. 5. Effect of pH on Cd(II) removal by adsorption and pre- more Hq from the activated carbon surface (Namasi-
cipitation. Conditions: carbon concentration 20 mgy50 ml; agi- vayam and Kadirvelu, 1997b).
tation time 1 h.
3.6. Desorption studies
saturated and adsorption begins on lower energy sites,
resulting in a decrease in the adsorption efficiency. Desorption studies were carried out to further eluci-
The conventional method for the removal of heavy date the mechanism of adsorption of Cd(II) (Fig. 6).
metals is by precipitation as hydroxides of sulfides. This Attempts were made to desorb Cd(II) from the carbon
method has the limitation that metal ions cannot be sources using different concentrations of HCl. The
completely removed from solution due to the value of maximum percentage recovery of Cd(II) was 100%
the solubility product constant of metal hydroxides or with 0.075 M HCl solution. This indicates that ion
sulfides. In the absence of carbon, precipitation of metal exchange is involved in the adsorption process.
hydroxide starts at pH 8.5. In the presence of carbon,
there is competition between carbon adsorption and 4. Conclusion
precipitation as metal hydroxide. The maximum adsorp-
tion of Cd(II) was observed below the pH of hydroxide Coirpith carbon is an effective adsorbent for the
precipitation. An increase in metal ion uptake with an removal of Cd(II) from aqueous solution. The faster
increase in pH was also noted by other researchers, adsorption kinetic data (Kad and Kp) may be useful for
such as by Corapcioglu and Huang (1987) for adsorp- environmental technologists in designing Cd(II)-con-
tion of heavy metals onto hydrous activated carbon, taining wastewater plants. The adsorption is metal ion

Fig. 6. Effect of HCl concentration on Cd(II) desorption.

K. Kadirvelu, C. Namasivayam / Advances in Environmental Research 7 (2003) 471–478 477

concentration- and pH-dependent. The adsorption capac- Johonson, B.B., 1990. Effect of pH, temperature and concen-
ity (Q0) was 93.4 mg Cd(II)yg at initial pH 5.0 for the tration on the adsorption of cadmium on goethite. Environ.
particle size 250–500 mm. The adsorption followed Sci. Technol. 24, 112–118.
both the Langmuir and Freundlich isotherm models. Kadirvelu, K, 2000. Preparation and Characterization of Coir-
pith Carbon and its Utilization in the Treatment of Metal-
Adsorption of Cd(II) appears to takes place by an ion
Bearing Wastewaters. Bharathiar University, Coimbatore,
exchange mechanism. Quantitative recovery of Cd(II) India. PhD thesis.
is possible from Cd(II)-loaded carbon. It would be Kadirvelu, K., Namasivayam, C., 2000. Agricultural by-prod-
useful for the economic treatment of wastewater con- ucts as metal adsorbents: sorption of lead (II) from aqueous
taining Cd(II) to use an agricultural by-product such as solutions onto coirpith carbon. Environ. Technol. 21,
coirpith as an adsorbent. 1091–1097.
Kumar, P., Dara, S.S., 1980. Modified barks for scavenging
Acknowledgments toxic metal ions. Indian J. Environ. Health 22, 196–202.
Langmuir, I., 1918. The adsorption of gases on plane surfaces
of glass, mica, and platinum. J. Am. Chem. Soc. 40,
Dr. K. Kadirvelu is grateful to the Council of Scien- 1361–1368.
tific and Industrial Research (CSIR), Government of Lopez, E., Soto, B., Arias, M., Nunez, A., Rubinos, A., Barnal,
India, for the award of Senior Research Fellowship. M., 1998. Adsorption properties of red mud and its use for
Author K.K would also like to express sincere thanks wastewater treatment. Water Res. 32, 1314–1322.
to Prof Ilango (Vice-Chancellor) and Prof V. Gopal Low, K.S., Lee, C.K., 1991. Cadmium uptake by the moss
(Head of Department of Environmental Sciences) Bhar- Claymepers delsrtii. Bioresour. Technol. 38, 1–6.
athair University, Coimbatore, India for their valuable Marshall, W.E., Johns, M.M., 1996. Agricultural by-product as
help and encouragement. metal adsorbents: sorption properties and resistance to
mechanical abrasion. J. Chem. Technol. Biotechnol. 66,
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