Separation and Purification Technology 47 (2006) 141147

Adsorption of Ni(II), Zn(II) and Fe(II) on modified coir fibres

S.R. Shukla , Roshan S. Pai, Amit D. Shendarkar
Department of Fibres and Textile Processing Technology, Institute of Chemical Technology,
University of Mumbai, Matunga, Mumbai 400019, India
Received 21 December 2004; received in revised form 23 June 2005; accepted 24 June 2005

Abstract
The potential of a cheap lignocellulosic fibre, coir was assessed for removal of heavy metal ions like Ni(II), Zn(II) and Fe(II) from their
aqueous solutions. The fibre was also chemically modified by oxidising it with hydrogen peroxide for use as adsorbent. Langmuir type
adsorption was followed by the coir fibres. The modified coir fibres gave higher metal ion uptake as 4.33, 7.88 and 7.49 mg/g for Ni(II),
Zn(II) and Fe(II), respectively, against 2.51, 1.83 and 2.84 mg/g for the unmodified coir fibres. The metal ion uptake values decreased
with lowering of pH. The desorption efficiency, regenerative and reuse capacity of these adsorbents were also assessed for three successive
adsorptiondesorption cycles. The adsorptive capacity was retained only when regeneration with dilute NaOH solution is carried out as an
intermediate step after desorption. An ion-exchange mechanism has been proposed for the enhanced metal ion uptake on modified coir.
2005 Elsevier B.V. All rights reserved.
Keywords: Adsorption; Coir; Heavy metal; Oxidation; Regeneration

1. Introduction
Heavy metals are continuously released into the aquatic
environment from natural processes like volcanic activity
and weathering of rocks. Industrial processes have greatly
enhanced the mobilisation of heavy metals. Excess heavy
metals are introduced into aquatic ecosystems as by-products
of industrial processes and acid-mine drainage residues. They
are highly toxic as ions or in compound forms; they are
soluble in water and may be readily absorbed into living
organisms [1]. After absorption, these metals can bind to vital
cellular components, such as structural proteins, enzymes and
nucleic acids, and interfere with their functioning. Due to the
stringent environmental laws or increased awareness of people about environmental aspects, treatment of the effluent
streams has got exceptionally great importance nowadays.
The removal of heavy metals as for the other pollutants from
effluents in an effective manner is the need of the day. Further, it is also possible to recover the metal ions n a suitable
manner.

Corresponding author. Tel.: +91 22 24145616; fax: +91 22 24145614.

E-mail address: sanjeevrshukla@rediffmail.com (S.R. Shukla).

1383-5866/$ see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.06.014

There are various established methods for the removal of

heavy metals. Generally, the techniques employed include
reduction and precipitation [2], coagulation, flotation [3],
adsorption on activated carbon [4,5], ion-exchange and
reverse osmosis or electrodialysis [6]. Out of these, the most
used are the reduction and precipitation as well as the coagulation techniques. These methods, however, are less efficient
and create sludge. Ion-exchange and reverse osmosis, even
though effective and efficient, are expensive, hence only few
industries think of it. Alternate methods, like adsorption on
agricultural/biological waste, have been employed by many
workers as those in references [711].
The agricultural waste mainly comprise of cellulose,
which is a natural biopolymer with ion-exchange property
[12]. Natural cellulosic materials are abundantly available,
very cheap and can be modified very easily. It has been shown
earlier that loading these cellulosic materials with dyestuffs
of specific chemical structure do enhance the adsorptive
capacity of these materials [13]. The present communication reports the results on adsorption of heavy metals like
Ni(II), Zn(II) and Fe(II) on coir, a lignocellulosic fibre. The
effect of oxidation of coir fibres with H2 O2 on the adsorptive capacity was also noted. The effect of pH, regenera-

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S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

tive and reusable capacity of the adsorbents has also been

assessed.

2. Experimental
2.1. Materials
Coir fibre waste, collected from a local industry was
cleaned with soap solution at boil, washed, dried and cut
into approximately uniform length of 1 cm.
2.2. Chemicals
NiSO4 7H2 O, Zn(NO3 )2 6H2 O and FeSO4 7H2 O were
the heavy metal salts. The other chemicals used, such as
hydrogen peroxide, propanol-2, sodium carbonate, sodium
hydroxide, were of analytical reagent grade supplied by
Merck (India) Ltd., Standards for AAS, 1000 ppm of each
metal ions was supplied by Merck (I) Ltd. Demineralised
water was used for the entire experiments.
2.3. Methods
2.3.1. Modication of coir bres
The aim was to oxidise the hydroxyl group of cellulose in coir to carboxyl group thus creating a weak cationic
ion-exchanger. The amount of hydrogen peroxide used was
higher than the amount used normally for the oxidative
bleaching of cellulosic fibre to get desired whiteness [14].
One hundred grams of the coir fibre was added to 2 L solution containing 15 g (50%) hydrogen peroxide and 1 g sodium
hydroxide (pH 10.5) at room temperature. The temperature was slowly raised to 85 C and oxidation was continued for 2 h. After this, the material was filtered, washed
thoroughly with hot water and then with cold water. The
material was then dried in an oven at 50 C and used as an
adsorbent.
2.3.2. Estimation of accessibility of coir bre
The method used for determining the accessibility of the
cellulosic materials is based on the displacement of water
with propanol-2 solvent that is retained without any swelling
of the material and allows the removal of extraneous liquid
by centrifuging. The procedure is explained elsewhere [15].
2.3.3. IR spectra
The IR spectrum of the unmodified and oxidised coir samples was recorded with Bomem Hartmann and Braun MB
Series FTIR Spectrophotometer. Samples of 100 mg potassium bromide containing 2% of finely ground powder of each
sample were prepared and subjected to analysis.
2.3.4. Estimation of acid groups in modied coir bre
Oxidation of a cellulosic material converts the hydroxyl
group to the carboxyl groups. The presence of these acidic

groups in oxidised coir was estimated using Methylene Blue

absorption method, which is commonly applied to cellulosic
materials in the field of textiles [1618]. The principle used is
that when the cellulosic material gets oxidatively degraded, as
in the case of bleaching, the carboxylic groups are generated.
Such material is treated with a standard solution of Methylene
Blue, a cationic dye. Coloured dye cation is quantitatively
absorbed and retained by carboxylate anion in the degraded
cellulose. One gram of oxidised coir was made cation free by
treating it with 1N HCl for 10 min at room temperature followed by washing and then treated with a solution containing
100 mL of 5 mM/L Methylene Blue, 15.625 mM/L potassium dihydrogen phosphate and 10 mM/L sodium hydroxide
for 18 h. The material was filtered and filtrate was subjected
to determination of colour value at max of 664.5 nm using
Techcomp UVvis Spectrophotometer, model 8500. A blank
experiment without any material was also run alongside and
the absorbance of this solution was determined. The drop in
the concentration the dye in the treating solution due to dye
uptake by coir sample was determined by referring to the calibration curve and the amount of carboxyl groups present in
the coir was calculated in terms of milliequivalents/100 g of
dry material.
2.3.5. Scanning electron micrograph
In order to study the morphological changes during
bleaching of coir, the samples before and after bleaching were observed under a Scanning Electron Microscope,
model Philips XL 30, The Netherlands. The coir fibres were
mounted on a specimen stub with double sided adhesive carbon tapes. The samples are very sensitive to electron beam
and the charging of the specimen causes artefacts and also
focusing problem in the SEM. To avoid the charging, the spec of conducting
imen was coated with a thin layer (250300 A)
material, viz., Au/Pd using Sputter Coater and examined
under SEM at 12 kV with an angle of 45 .
2.3.6. Adsorptiondesorption studies
Metal ion adsorption isotherms were developed for
unmodified and modified coir fibres from solutions that
ranged in concentration from 82.3 to 456.6 mg/L of Ni(II),
73.5 to 444.8 mg/L of Fe(II) and 38.2 to 212.6 mg/L of Zn(II).
One gram of the material was shaken in a flask containing
50 mL of metal ion solution at a constant temperature of
35 C, using a flask shaker for predetermined equilibrium
time of 120 min [23]. The material was then filtered and the
residual solution was analysed for estimating the metal ion
concentration using Atomic Absorption Spectrophotometer
(Model 932 Plus, GBC, Australia). The standards for analysis were prepared from stock solutions of 1000 ppm supplied
by Merck (I) Ltd.
All the experiments were repeated five times and the average values have been reported. Also, blank experiments were
conducted to ensure that no adsorption was taking place on
the walls of the apparatus used.

S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

Langmuir adsorption is given by the equation:

1
1
1 1
=
+
Qeq
Q0
bQ0 Ceq
where Qeq is equilibrium metal ion uptake (mg/g), Ceq the
equilibrium concentration in solution (mg/L), Q0 represents
the maximum uptake of metal ion (mg/g) and b is a constant
related to the energy of adsorption (L/mg)
Freundlich adsorption is:
1
log Ceq
n
where Kf is the proportionality constant and n is a dimensionless exponent related to energy of adsorption.
Initial metal ion concentrations of 74.00, 73.50 and
83.9 mg/L were used for Ni(II), Zn(II) and Fe(II), respectively, for experiments conducted at different pH. The parameters of adsorption were determined at respective pH of the
aqueous metal salt solutions, viz., Ni(II) at 6.5, Zn(II) at 5.87
and Fe(II) at 4.75. Experiments were also conducted at different pH by adjusting the initial pH to the lower ones by using
appropriate acids. Thus, initial pH of 6.5 of Ni(II) solution
was adjusted to 3.5, 2.2 and 1.0 and that of Zn(II) of 5.87
was adjusted to 3.0 and 1.5 by using 0.25N nitric acid. The
initial pH of Fe(II) of 4.75 was adjusted to 3.0 and 1.5 by
using 0.25N sulphuric acid.
Desorption of the Ni(II) and Zn(II) from each of the loaded
material was carried out by shaking them with 50 mL of
0.25N nitric acid, whereas for Fe(II), 0.25N sulphuric acid
was used at 35 C for 120 min. The metal ion contents of
the desorbed acid solutions were estimated using Atomic
Absorption Spectrophotometer.
log Qeq = log Kf +

2.3.7. Regeneration of coir samples

The coir samples after desorption of metal ions were thoroughly washed with demineralised water and were given a
treatment with 50 mL of 0.5 g/L NaOH solution for 60 min.
This was followed by washing again with demineralised
water, drying and reusing the material for adsorption. The
experiment was also carried out without treatment with
NaOH.

3. Results and discussion

3.1. Characteristics of the coir bres
Coir possesses substantial amount of cellulose (43.44%),
which is a natural polymer made up of -glucose units with
abundant primary and secondary hydroxyl groups. It also possesses lignin (45.84%), having a network type of structure
with majority of methoxy and free hydroxyl groups [19]. Both
these chemical entities in coir have been shown to be capable
of adsorbing various types of heavy metal ions [20,21]. This
adsorption was observed to be of ionic nature and even dilute
acids are capable of fully desorbing them. In the present study,

143

Table 1
Characteristics of coir and oxidised coir
Material

Propanol-2 retention (%)

Acid groups (meq/g)

Coir fibres
Oxidised coir

19.12
44.56

0.0704
0.2121

coir was subjected to a chemical modification by oxidation

using hydrogen peroxide. Both unmodified and modified coir,
cut uniformly, were used as adsorbents.
The isopropanol-2 retention values for unmodified and
oxidised coir are given in Table 1. This technique of accessing the openness of the cellulosic materials has since long
been used for estimating their swelling caused by various
inter crystalline swelling agents [22]. The key factor is that on
treating cellulosic material with a swelling agent, the polymer
structure opens up due to breaking of inter-chain hydrogen
bonds in the amorphous region of the polymer and moves
the polymer chains apart. Propanol-2 simply imbibes in by
displacing the swelling agent without altering the swollen
structure. The technique, therefore, gives precise understanding about the changes in the openness of material, more or
less in a comparative manner, caused due to any modification. In the present case, it is expected that apart from the
chemical nature of the adsorbing material, the openness or
accessibility of its physical structure also has an important
role to play in allowing the metal ions to be adsorbed on the
external as well as internal crystallite surfaces of the polymer
by penetration. The data in Table 1 indicates that the oxidised
coir has more accessibility than the unmodified one. This can
also be observed from the SEM of unmodified and oxidised
coir. It can be seen from Fig. 1 that the oxidised coir has more
number of pores, which have opened up when compared to
the unmodified coir.
Oxidation of the cellulosic part in coir causes its degradation leading to chain scission and generation of carboxyl
groups. The lignin component upon the oxidation gives rise
to water-soluble dicarboxylic acids. Overall, the oxidation
of coir led to loss in the strength, although not high enough
to distort the physical (fibrous) form of coir. The carboxyl
groups of oxidised coir are capable of quantitative absorption of Methylene Blue. From Table 1, it is also clear that the
oxidised coir fibres do possess anionic groups, where as in
the case of unmodified coir, they are almost negligible.
Fig. 2 gives the IR plot of unmodified coir fibres. On oxidation with H2 O2 , an additional a peak at 1735.34 cm1 was
observed, which is characteristic of the carbonyl group of
COOH.
3.2. Adsorption isotherms
The adsorption isotherms of different metal ions on coir
are depicted in Fig. 3. The adsorption studies are characterised by Langmuir or Freundlich adsorption models. The
application of Langmuir model to the experimental equilibrium isotherm data for the adsorption of different metal ions

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S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

Fig. 1. SEM photographs of coir samples.

on to the unmodified and oxidised coir yields two parameters, the maximum adsorptive capacity, Q0 and a constant
related to the energy of adsorption, b. Freundlich treatment
gives the parameters, n, indicative of bond energies between
metal ion and the adsorbent and Kf , related to bond strength.
These values along with the determination coefficient, R2 ,
values for Langmuir and Freundlich isotherm for adsorption
of the Ni(II), Zn(II) and Fe(II) on the two adsorbents are

Fig. 2. IR Plot of coir fibre.

Fig. 3. Adsorption isotherms of different metal ions on coir fibres. ()

Adsorption of Ni(II) on coir fibres; (
) adsorption of Ni(II) on oxidised
coir fibres; () adsorption of Zn(II) on coir fibres; () adsorption of Zn(II)
on oxidised coir fibres; () adsorption of Fe(II) on coir fibres; () adsorption
of Fe(II) on oxidised coir fibres.

S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

145

Table 2
Different parameters derived from Langmuir and Freundlich adsorption isotherms
Metal ion

Adsorbent

R2 -values
Langmuir

Freundlich

Q0 (mg/g)

b (L/mg)

Kf (mg(1(1/n)) L1/n /g)

Ni(II)

Coir
Oxidised coir

0.9007
0.9987

0.8544
0.9336

2.51
4.33

0.0112
0.0029

2.61
3.88

0.21
0.91

Zn(II)

Coir
Oxidised coir

0.9557
0.9653

0.9715
0.9604

1.83
7.88

0.1129
0.0310

5.39
1.74

0.71
0.49

Fe(II)

Coir
Oxidised coir

0.9734
0.9812

0.8721
0.9758

2.84
7.49

0.0180
0.0362

3.50
3.05

0.46
1.15

given in Table 2. The R2 -values for the adsorption of all the

three metal ions were above 0.96 in the case of oxidised coir,
which reveal the extremely good applicability of the Langmuir model to these adsorptions. In the case of unmodified
coir also, R2 -values were higher for the Langmuir fit. Such
values for the Freundlich fit indicated a somewhat poorer fit
to the experimental data when compared with the Langmuir
treatment.
In all the cases, higher Q0 values of 4.33 mg/g (0.07 mM/g)
for Ni(II), 7.88 mg/g (0.12 mM/g) for Zn(II) and 7.49 mg/g
(0.13 mM/g) for Fe(II) adsorption were observed for the oxidised coir adsorbent. The differences in the actual Q0 values
for the different metal ions may be attributed to the differ
ences in the ionic radii. The ionic radius of Ni(II) is 69 A,
for Zn(II) and Fe(II). The b values were
where as it is 74 A
higher for unmodified coir in the case of Ni(II) and Zn(II),
which indicate a stronger affinity of these metal ions to coir,
where as in the case of Fe(II), it was observed to be higher
for the oxidised coir.
3.3. Mechanism of adsorption of metal ions
The increase in the adsorption of metal ions in the case
of oxidised coir may be attributed to the formation of carboxylic acid group due to oxidation treatment. The oxidation
process using hydrogen peroxide was carried out in an alkaline medium (pH 10.5) and hence these carboxyl groups also
will be in the form of their sodium salt. The metal ion adsorption on oxidised coir, based on ion-exchange mechanism can
be expressed as:
2 Coir COONa + M2+ (Coir COO)2 M + 2Na+
Thus, metal ion replaces the Na cation.
3.4. Effect of pH on adsorption of metal ions
Fig. 4 depicts the effect of pH on the adsorption of
metal ions on unmodified and oxidised coir fibres. It may
be observed that the adsorption for all the three metal ions
studied decreased with the lowering of pH. Thus, Ni(II) ions
having a maximum adsorption of 26.09% at pH 6.5 showed a
progressive decrease to 16.21% at a pH of 3.5, 7.79% at pH of
2.2 and finally 3.78% at a pH of 1.0 for the unmodified coir.
The respective values for the oxidised coir were found to be

Fig. 4. Effect of pH on adsorption of different metal ions on coir fibres. ()

Adsorption of Ni(II) on coir; (
) adsorption of Ni(II) on oxidised coir; ()
adsorption of Zn(II) on coir; () adsorption of Zn(II) on oxidised coir; ()
adsorption of Fe(II) on coir; () adsorption of Fe(II) on oxidised coir.

56.89, 24.32, 14.98 and 6.89%. Similar trend was observed

for Zn(II) and Fe(II) adsorption, although the actual values
differed. Thus, at lower pH, the adsorption of heavy metal
ions studied was substantially reduced. This observation was
made use of to desorb the metal ions from the adsorbed materials by using acids as eluents.
3.5. Repeated adsorptiondesorption studies
The adsorption and desorption efficiencies of the modified
adsorbents are summarised in Table 3. It may be observed that
the desorption is quite high even for unmodified coir whereas
with oxidised coir it is nearly complete for Zn(II) and Fe(II)
ions.
The coir samples were then subjected to
adsorptiondesorption cycles through regeneration step
in-between. It can be clearly observed from the data in
Table 4 that the efficiency of adsorption was retained only
when the materials after desorption were given a treatment
with 0.5 g/L sodium hydroxide solution. When the desorbed
materials were reused without such intermediate treatment,
there was in fact a decrease in the adsorptive capacity for the
materials.
Thus, Ni(II) ions showed 26.09% adsorption on unmodified coir, which decreased to 12.32% when it was sub-

S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

146

Table 3
Adsorption and desorption of different metal ions on coir samples
Metal ion

Adsorbent

Metal ion concentration

Initial bath (mg/L)

Final bath (mg/L)

Adsorbed (mg/g)

Adsorbed (%)

Desorbed (%)

Ni(II)

Coir
Oxidised coir

74.00

54.69
31.90

0.97
2.11

26.09
56.89

78.71
81.99

Zn(II)

Coir
Oxidised coir

73.5

47.50
16.80

1.30
2.84

35.37
77.14

89.80
93.47

Fe(II)

Coir
Oxidised coir

83.90

53.10
26.50

1.54
2.87

36.71
68.41

89.35
96.60

jected only to washing with water after desorption. However, when the desorbed coir was subjected to regeneration using NaOH, the readsorption values were 25.89, 26.05
and 24.56% after each of the three desorptionadsorption
cycles indicating nearly same adsorption as of the original
material.
Lowering of pH during adsorption of metal ions on to
cellulosic materials is due to the release of H+ ions from
cellulose into the solution [23]. The desorption occurs by
the replacement of metal ions by H+ ions from the eluting
acid. It can be seen that there was a substantial lowering
of pH after adsorption, as indicated in Table 4. When the
desorbed materials were subjected to readsorption, the drop in
pH was still higher. This may be due to the replacement of H+
ions by the metal ions from the materials. This phenomenon
also has an effect of decreasing the adsorption as shown in
Fig. 4. In the case of desorbed materials regenerated with
sodium hydroxide solution, Na+ is released into the solution
during readsorption. The oxidation of coir fibres has been
carried out in alkaline medium resulting in the formation
of sodium salt of carboxylic acid groups. The difference in
pH before and after adsorption was found to be nominal in
the case of oxidised coir adsorbent when it was used in the
first adsorption cycle. Hence, a loading with Na+ is required
after desorption and washing to retain the materials original
adsorption capacity. Thus, the modified coir fibre can be used
as a reversible ion-exchanger.

Table 5
Comparison of metal ion adsorption capacities of different adsorbents
Adsorbent

Adsorption capacity
(mg/g) of

Dye loaded groundnut shell

Dye loaded sawdust
Cork biomass
Plant compost
Dyestuff treated rice hull
Wheat bran
Turkish coal
Flyash
Pine bark waste
Crosslinked chitosan
Coir
Oxidised coir

Ni(II)

Zn(II)

7.49
9.87
44.60
0.30
6.16
12.00

2.51
4.33

9.57
17.09
22.22
1.23

1.2
0.75

1.83
7.88

References
Fe(II)

2.03
64.10
2.84
7.49

[15]
[15]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
This work
This work

Table 5 gives the maximum capacities of different adsorbents for he removal of Ni(II), Zn(II) and Fe(II) from aqueous
solutions. It can be seen that maximum adsorptive capacities
for these metal ions were different for different materials
used. This will depend on the physical nature and chemical
composition of the materials used from removal of metal ions.
In the present work, an oxidative modification was given to
coir fibres. Since it makes use of hydrogen peroxide, it essentially is a modification, which does not add to pollution load.

Table 4
Adsorption of metal ions on regenerated coir samples
Metal
ion

Ni(II)

Zn(II)

Fe(II)

Adsorbent

Coir
Oxidised
coir
Coir fibres
Oxidised
coir
Coir
Oxidised
coir

Adsorption step
Initial
Concentration
(mg/L)

Adsorbed
(%)

74.00

26.09
56.89

83.9

73.5

Regeneration step (metal ion adsorbed (%))

pH

Without
NaOH

Initial
bath

With NaOH
Cycle 1

Cycle 2

Cycle 3

X S.D.

12.32
35.12

25.89
58.19

26.05
55.84

24.56
56.81

25.50 0.67
56.95 0.94

6.50

36.71
68.41

22.15
49.86

35.65
69.53

38.21
68.52

36.12
67.89

36.66 1.11
68.65 0.68

35.37
77.14

28.81
38.77

37.14
77.55

35.78
76.84

37.10
76.17

36.67 0.63
76.85 0.56

Final
bath

Of final bath after adding

desorbed material
Without
regeneration

With
regeneration

5.02
6.41

4.56
4.85

5.09
6.38

5.87

4.32
4.80

3.65
4.06

4.33
4.76

4.75

4.21
4.70

3.20
2.60

4.30
4.60

S.R. Shukla et al. / Separation and Purication Technology 47 (2006) 141147

4. Conclusion
The oxidised coir fibres possess more efficiency than the
unmodified coir in adsorbing metal ions like Ni(II), Zn(II)
and Fe(II) from their aqueous solutions. The enhancement in
the metal ion uptake in the case of oxidised coir is due to the
generation of carboxylic acid groups in the coir fibre. The
adsorption of these metal ions on to coir fibres is governed
by Langmuir type isotherm. Both unmodified and oxidised
coir showed a decrease in adsorption with lowering of pH.
The materials can be regenerated using alkali and can be
reused with fullest efficiency for at least up to three times,
thus enhancing their reusability, hence acting like a reversible
ion-exchanger. The metal ion concentrations used are of sufficiently high order and the batch experiments have indicated
a very good potential of higher levels of adsorption and
desorption when modified materials are used as adsorbents.
The oxidative treatment of coir is quite cost effective and
ecofriendly.
Acknowledgement
The authors greatfully acknowledge the financial support
given by Ministry of Environment and Forests, Govt. of India,
New Delhi.
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