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Applied Clay Science 31 (2006) 298 305

www.elsevier.com/locate/clay

Removal of heavy metal ions by dithiocarbamate-anchored


polymer/organosmectite composites
Rdvan Say a,b,, Ebru Birlik c , Adil Denizli d , Arzu Ersz a
a
Department of Chemistry, Anadolu University, Eskiehir, Turkey
b
BIBAM (Plant, Drug and Scientific Researches Center), Anadolu University, Eskiehir,Turkey
c
Department of Chemistry, Osmangazi University, Eskiehir, Turkey
d
Department of Chemistry, Hacettepe University, Ankara, Turkey
Received 8 February 2005; received in revised form 9 September 2005; accepted 6 October 2005
Available online 23 November 2005

Abstract

In this study, the dithiocarbamate-anchored polymer/organosmectite composites were prepared for the removal of heavy metal
ions (lead, cadmium and chromium) from aqueous media containing different amounts of these ions (50750 ppm) and at different
pH values (2.08.0). Initially, the modification of the natural smectite minerals was performed by treatment with quartamin styrene
and chloromethylstyrene. Then, modified smectite nanocomposites were reacted with carbondisulfide, in order to incorporate
dithiocarbamate functional groups into the nanolayer of organoclay. The dithiocarbamate-anchored nano-composites have been
characterized by FTIR and used in the adsorptiondesorption process. The maximum adsorptions of heavy metal ions onto the
dithiocarbamate-anchored polymer/organosmectite composites from their solution was 170.7 mg g 1 for Pb(II); 82.2 mg g 1 for
Cd(II) and 71.1 mg g 1 for Cr(III). Competition between heavy metal ions (in the case of adsorption from mixture) yielded
adsorption capacities of 70.4 mg g 1 for Pb(II); 31.8 mg g 1 for Cd(II) and 20.3 mg g 1 for Cr(III). Desorption of the heavy metal
ions from composite was studied in 0.5 M NaCl and very high desorption rates, greater than 93%, were achieved in all cases.
Adsorptiondesorption cycles showed the feasibility of repeated uses of this nanocomposite.
2005 Elsevier B.V. All rights reserved.

Keywords: Heavy metal ions removal; Organoclay; Nanocomposite; Smectite

1. Introduction followed by recovery or secure disposal. Different treatment


techniques have been developed to remove either or both
The presence of heavy metals in the environment has dissolved and suspended heavy metal ions from industrial
been of great concern because of their growing discharge, waters and wastewaters. Nonspecific sorbents, such as acti-
toxicity and other adverse effects on receiving waters. Treat- vated carbon, metal oxides, and ion-exchange resins have
ment of aqueous wastes containing soluble heavy metals been used (Rodrigues, 1986; Reed and Matsumoto, 1993).
requires concentration of the metals into a smaller volume Specific sorbents consist of a ligand (e.g., ion-exchange
material or chelating agents) which interacts with the metal
Corresponding author. Anadolu niversitesi, Fen Fakltesi,
ions specifically, and a carrier matrix which may be an
Kimya Blm, Yunus Emre Kamps, 26470-Eskiehir, Turkey. inorganic material (e.g., aluminum oxide, silica or glass or
Tel./fax: +90 222 320 4910. polymer microspheres (e.g., polystyrene, polymethlmetha-
E-mail address: rsay@anadolu.edu.tr (R. Say). crylate, cellulose) have been considered for more specific
0169-1317/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2005.10.006
R. Say et al. / Applied Clay Science 31 (2006) 298305 299

removal (Kaneko and Tsuchida, 1981; Myasoediva and The smectite used troughout study was obtained from
Savvin, 1986; Kantipuly et al., 1990; Pikin et al., 1996; Northern Anotolia, Turkey and was crushed and sieved to
Salih et al., 1998; Say et al., 1998, 2002). have particles of size 200 m. The chemical and some physical
Some naturally occuring clay minerals may serve as properties of simectite are given by Arpa et al. (Arpa et al.,
2000).
cost-effective sorbents for the removal of heavy
metals. While their sorption capacity is usually less 2.2. Instrumentation
than those of synthetic sorbents, these materials could
provide an expensive substitute for the treatment of A Hitachi 180-70 polarized Zeeman atomic absorption
heavy metal waste waters. To enhance the sorption spectrophotometer with deuterium background correction
capacity, the clays are modified in various ways, was used for the determination of Pb(II), Cd(II) and Cr(III).
such as treatment by inorganic and organic com- Pb(II), Cd(II) and Cr(III) absorbance mesaurements were
pounds, acids and bases (Erdemolu et al., 2004; made at 283.3, 228.8 and 357.9 nm using a Hitachi hollow
Vengeris et al., 2000; Lothenbach et al., 1997; Malakul cathode lamp operating at 7.5 mA.
Jenway 3100 pH-meter was used to mesaure pH values.
et al., 1998; Curkovic et al., 1997; Qi and Dingxue,
1997; Ruiz et al., 1997). 2.3. Preparation of dithiocarbamate-anchored polymer/orga-
Organoclays have recently attracted much attention nosmectite composites
in a number of applications, such as polymer-clay nano-
composites (Tseng et al., 2001; Voulgaris and Petridis, The organoclay was prepared by the similar way as
2002; Tabtiang et al., 2000), absorbents of organic pol- decribed by Tabtiang et al. (Tabtiang et al., 2000). The simec-
lution in ground water, coating and paints (El-Nahhal tite (20 g) was dispersed in deionized water (500 mL) at 80 C.
and Safi, 2004). Composites have been prepared A solution of quartamin[dimethyl(dihydrogenated tallow)am-
through in situ polymerisation of monomers within the monium chloride] (0.05 mol) and concentrated HCl (5 mL) in
galleries of modified clays (Messersmith and Giannelis, deionized water (100 mL) was added; heated and stirred for 3
h. The suspension was filtered, and the solid residue washed
1995) and through intercalation from solution (Gianne-
with hot distilled water until no chloride was left. The product
lis, 1996). It has been reported that several of these
was dried at 55 C for several days in a fan oven, then dried
composites exhibited improved mechanical (Lee and under vacum for 24 h, yielding the quartamin modified simec-
Jang, 1996) and barier properties (Yano et al., 1997), in tite (QS). For the preparation of polymer/quartamin modified
comparison with the matrix polymer. simectite (PQS), the following experimental procedure was
In this study, the dithiocarbamate-anchored polymer/ applied; AIBN (0.1 g) was dissolved in the extracted styrene
organosmectite composites was used to remove heavy (12 mL) and 50 mL of distilled hexane was needed to disperse
metal ions from aqueous solutions. Firstly, naturally the QS. The reaction flask was suspended in a thermostated
occuring smectite minerals was modified with quarta- water bath at 65 C for 9 h and then added into the flask
min, styrene and chloromethylstyrene. Secondly, the containing 3 mL of chloromethylstyrene, 0.050 g AIBN and
quartamin and polystyrenestyrene modified smectite 20 mL hexane in the same bath and stirred for 24 h. The
quartamin and modified smectite nanocomposites were
nanocomposites were reacted with carbondisulfide, in
cleaned and a two-step procedure was applied in order to
order to incorporate dithiocarbamate functional groups
incorporate dithiocarbamate functional groups into the subsur-
into the subsurface of organoclay. Finally, these compo- face of organoclay (Pikin et al., 1996). Firstly, 10 g of the
sites were used in adsorptiondesorption studies. Heavy nanocomposites were added into the mixtures of 50 mL water
metal adsorption on the dithiocarbamate-anchored poly- and 1.5 mL benzylamine and the resulting suspensions were
mer/organosmectite composites from aqueous solutions stirred at a stirring rate of 600 rpm at 20 C for 24 h. Then the
containing their different amount at different pHs and amine groups of benzylamine were transformed into dithiocar-
selectivity studies were investigated. Finally, repeated bamate groups by reacting with carbon disulfide. The nano-
use of the dithiocarbamate-anchored composites from composites containing benzylamine were added into the
water was also discussed. mixtures of 50 mL water and 4.0 mL of 1,4-dioxane, and the
pH of the media were rapidly adjusted to 11 by using 1.0 M
KOH. 4.0 mL carbon disulfide was then added to these media,
2. Experimental and the resulting mixture was stirred at 20 C for 24 h, in order
to complete the reaction between benzylamine and carbon
2.1. Materials disulfide. The solid, powdered product was recoverd from the
reaction mixture by evaporation of the solvent, followed by
Azobisisobutyronitrile (AIBN) was obtained from Fluka. drying under vacuum at 55 C. Incorporation of dithiocarba-
All other chemicals were reagent grade and purchased from mate groups into nanolayer of the organosimectite was inves-
Merck (Darmstadt,Germany). tigated by using FTIR.
300 R. Say et al. / Applied Clay Science 31 (2006) 298305

2.4. Heavy metal adsorptiondesorption studies

Heavy metal ion adsorption from the single metal aque-


ous solutions was investigated in batch experiments. Effects
of the initial heavy metal concentration and pH of the
medium on the adsorption rate and adsorption capacity
were studied. The suspensions were brought to the desired
pH by adding sodium hydroxide and nitric acid. The pH was
maintained in a range of 0,1 U until equilibrium was
attained. In all experiments, polymer concentration was
kept constant at 25 mg/25 mL. The concentration of the
metal ions in the aqueous phases after desired treatmant
periods were measured by using a flame atomic absorption
spectrophotometer (FAAS) and deuterium background cor-
rection was used. The instrument response was periodically
checked with known heavy metal solution standarts. For
each sample, the mean of 10 AAS measurements was
recorded. The amount of adsorbed heavy metal ions was
calculated using the following equation:

Q Co CA :V =m: 1

Where Q is the amount of metal ions adsorbed onto unit


amount of the composites (mg g 1); Co and CA are the con-
centrations of metal ions in the initial solution and in the
aqueous phase after adsorption, respectively (mg mL 1); V
is the volume of the aqueous phase (mL); and m is the weight
of the composites (g).
Competitive adsorption of heavy metal ions from their
mixture was also investigated in a batch wise form. A solution
Fig. 1. IR spectrum of a) orginal smectite minerals, b) organosmectite,
(25 mL) containing 50 and 100 mg/L from each metal ions
c) dithiocarbamate-anchored polymer/organosmectite composite.
was treated with the 25 mg nanocomposites at a pH 6.0 at
room temperature, in the flask stirred magnetically at 600 rpm.
After adsorption equilibrium, the concentration of metal ions FTIR spectra of organosmectite (Fig. 1-b) is given
in the remaining solution was mesaured by a FAAS system.
below: NH stretching in the 3400 cm 1, CH stretch-
In order to determine the reusability of the nanocompo-
sites, consecutive adsorptiondesorption cycle were repeated
ing in the 2920 cm 1, CH (concerning CH2 group)
five times using the same composites. Desorption of heavy stretching in the 2840 cm 1 and CCl stretching in the
metal ions was achieved using 0.5 M NaCl. The nanocompo- 800 cm 1. FTIR spectra of dithiocarbamate-anchored
sites carrying 38.1 mg g 1 Pb(II), 29.1 mg g 1 Cd(II) and 22.8 polymer/organosmectite composite (Fig. 1-c) is given
mg g 1 Cr(III) were placed in this desorption medium and below: NH stretching in the 3300 cm 1, CH stretch-
stirred at 600 rpm for 60 min at room temperature. The final ing in the 2920 and 2840 cm 1, C = C stretching in the
metal ion concentration in the aqueous phase was determined 1500 cm 1, CN stretching in the 1560 cm 1, C = S
using an atomic absorption spectrophotometer (AAS). The stretching in the 1180 cm 1 and CCl stretching in the
desorption ratio was calculated from the amount metal ions 800 cm 1. That is to say, organoclay has changed to
initially loaded on the composites and the final metal ion polymer/organo nanocomposite.
concentrations in the desorption medium.
3.2. Heavy metal adsorption
3. Results and discussion
3.2.1. Adsorption rate
3.1. Characterization of dithiocarbamate-anchored Fig. 2 examplifies adsorption rates of heavy metal
polymer/organosmectite composites ions by composites as a function of time. The figure
shows the changes in the metal ions adsorbed over time,
Fig. 1 shows IR spectrum of orginal smectite miner- which were calculated by using the expression given in
als, organosmectite containing chloromethylstyrene and Eq. (1). Note that these batch experiments were per-
styrene and polymer/organosmectite. formed by using single (not multiple) solutions of the
R. Say et al. / Applied Clay Science 31 (2006) 298305 301

reasonable comparison of the adsorption rates reported.


But, it can be said that, considering above results, we
have relatively good equilibrium time.

3.2.2. Effect of initial concentration of heavy metal ions


The heavy metal ion adsorption capacities of
the dithiocarbamate-anchored polymer/organosmectite
composites are given as a function of initial concentra-
tion of heavy metal ions within the aqueous phase in
Fig. 3. These adsorption curves were obtained from
Fig. 2. Adsorption rates of heavy metal ions by dithiocarbamate-
experiments where adsorptions from the single heavy
anchored polymer/organosmectite composites. Adsorption condi-
tion: initial concentration of metal ions, 50 mg/L; pH, 6; temper- metal aqueous solutions were studied. It was observed
ature, 20 C. that the amount of adsorption was significantly in-
creased with initial heavy metal concentration especial-
ly in the case Pb(II) and also for Cd(II) and Cr(III), in
ions of interest. Adsorption conditions are given in the the studied concentration range. The maximum adsorp-
figure legend. It should be noted that there was no tion capacities of the dithiocarbamate-anchored poly-
precipitation in these groups of experiments under the mer / organosmectite composites in the studied range
concentration and pH condition studied. As seen from are 170.7, 82.2 and 71.1 mg g 1 for Pb(II), Cd(II) and
Fig. 2 high adsorption rates were observed at the begin- Cr(III), respectively, at pH 6.0, which corresponds to an
ning, and then platue values (i.e., adsorption equilibri- initial concentration of 500 ppm. The affinity order
um) are gradually reached within 1525 min. (weight basis) is Pb(II) N Cd(II) N Cr(III).
Various experimental data on the adsorption kinetics It should be noted that the maximum adsorption
of heavy-metal ions by various sorbents have shown a capacities (molar basis) of the dithiocarbamate-an-
wide range of adsorption rates (Reed and Matsumoto, chored polymer/organosmectite composites are 823.84,
1993; Konishi et al., 1993; Hoins et al., 1993; Syamal 731.31 and 1367.30 mol g 1 of polymer for Pb(II), Cd
and Singh, 1993). For example, Reed and Matsumoto (II) and Cr(III), respectively. The order of affinity based
considered 6 h to be a short equilibrium time in their on micromole uptake by the sorbent differs according to
metal ions adsorption kinetics studies, in which have weight base and is as follows:
used activated carbon as sorbent (Reed and Matsumoto,
1993). Murty and Ryan have investigated mercury, cop- CrIIINPbIINCdII:
per, cadmium, lead and uranium adsorption on cellu- Erdemolu et al. was studied the adsorption of Pb(II)
losedithiocarbamate resins and reported that the ions on modified pyrophyllite and reported maximum
adsorption rates were slow, but they were able to use a adsorption Pb(II) ions on modified pyrophyllite was at
30 min equilibrium time reproducibly (Murty and Ryan, pH about 6.5 and at an initial concentration of 20 mg/L
1982). Chakravarty et al. have studied copper removal (Erdemolu et al., 2004).
from aqueous solution by hematite and reported an During the batch experimets, adsorption isotherms
equilibrium time of 75 min (Chakravarty et al., 1998). were used to evaluate adsorption properties. For the
Arpa et al.have investigated lead, cadmium and copper
adsorption on smectite and reported 30 min equilibrium
adsorption time (Arpa et al., 2000).
Note that such an adsorption process, there are sev-
eral parameters which determine the adsorption rate:
agitation rate in aqueous phase, sorbent structural prop-
erties (e.g., size, porosity, surface area), amount of
sorbent, metal ion properties (e.g., hydrated ionic radi-
us), initial concentration of metal ions, pH, temperature
and of course, the existence of other ions which may
compete with the ions of interest for active adsorption
sites. All individual experimental studies published in
the literature have been performed under different con- Fig. 3. Heavy metal ions adsorption capacity of the dithiocarbamate-
ditions. Consequently, it is not possible to make a anchored composites. Temperature 20 C; pH 6.0.
302 R. Say et al. / Applied Clay Science 31 (2006) 298305

organosmectite composites, indicating that the Lang-


muir adsorption model can be applied in this adsorbent
system. In this study, the maximum adsorption capacity
(Qmax) was found to be 714.28 mol/g (80.28 mg/g) for
Cd(II) from the Langmuir model. In the study of Loi-
dero et al. related to cadmium binding equilibria, the
maximum metal uptake was found to 65, 95 and 99 mg/
g for the raw biomass, protonated biomass and formal-
Fig. 4. Adsorption isotherm of heavy metal ions on the dithiocarba- dehyde biomass, respectively (Loidero et al., 2004).
mate-anchored composites. Temperature 20 C; pH 6.0.
3.2.3. Effect of pH
systems considered, the Langmuir adsorption model Metal ion adsorption onto non-specific and specific
was found to be applicable in interpreting Pb(II), Cd sorbents is pH dependent (Denizli et al., 1996, 1997).
(II) and Cr(III) adsorption by the dithiocarbamate-an- In the absence of complexing agents, the hydrolysis
chored polymer/organosmectite composites. The Lang- and precipitation of metal ions are affected by the
muir adsorption isotherm is expressed by Eq. (3). The concentration and form of soluble metal species. The
corresponding transformations of the equilibrium ad- solubility of metal ions is governed by hydroxide or
sorption data for Pb(II), Cd(II) and Cr(III) ions gave carbonate concentration. As discussed in detail by
rise to a linear plot, indicating that the Langmuir model Reed and Matsumoto (Reed and Matsumoto, 1993),
be applied in this system and described by Eq. (2). the hydrolysis of metal ions becomes significant at a
pH of approximately 7.58.5. Therefore, in this study
Q Qmax bCeq =1 bCeq 2 the pH range was adjusted to between 2.0 and 8.0.
Where Q is the concentration of adsorbed metal (Pb The effect of pH on heavy metal adsorption is illus-
(II), Cd(II) and Cr(III) ions) on the adsorbent (mmol/g), trated in Fig. 5. It was noticed that the adsorption
Ceq is the equilibrium ion (Pb(II), Cd(II) and Cr(III)) capacities increased with increasing pH, reaching pla-
concentration in solution (mg/l), b is the Langmuir teau values at around pH 46 depending on the metal
constant (l/mg) and Qmax is the maximum adsorption ions (Chwastowka and Kosiarska, 1988). Our plateau
capacity (mmol/g). This equation can be linearized so values are 38.1 for Pb(II), 28.4 for Cd(II) and 22.4 Cr
that (III) mg g 1, which correspond to initial metal ion
concentrations of 50 ppm.
1=Q 1=Qmax b1=Ceq  1=Qmax : 3 In this study, maximum adsorption of Cd(II) and Pb
(II) ions on the dithiocarbamate-anchored polymer/
From the plot of 1 / Ceq versus 1 / Q was employed to organosmectite composites was reported at pH 6.0 and
generate the intercept of 1 / Qmax and the slope of 1 / adsorption time was found 20 min for Cd(II) ions, 15
Qmaxb (Fig. 4). Fig. 4 shows Langmuir fitted data, min for Pb(II) ions. Loidero et al. was investigated
corresponding to heavy metal adsorption by the dithio- cadmium binding equilibria of dead biomass from sea-
carbamate-anchored polymer/organosmectite compo- weed Sargassum muticum and cadmium uptake capac-
sites at pH 6.0. The adjustable obtained parameters ity was found for pH higher than 4.5 and adsorption
(Qmax, b and n) are listed in Table 1. The maximum time for 45 min (Loidero et al., 2004). Erdemolu et al.
adsorption capacity (Qmax) of Pb(II), Cd(II) and Cr(III)
ions was obtained from experimental data. The correla-
tion coefficient (R2) was found to be very high, 0.9581,
0.9198, 0.9545 for Pb(II), Cd(II) and Cr(III) ions,
respectivly, for the dithiocarbamate-anchored polymer/

Table 1
Adsorption parameters of Langmuir isotherm equation at pH 6.0
Isotherm Qmax (micromol/g) b (L/mg) R2
Pb(II) 714.28 0.0281 0.9581
Fig. 5. Effect of pH on adsorption of heavy metal ions on the dithio-
Cd(II) 714.28 0.0255 0.9198
carbamate-anchored composites. Temperature 20 C. Intial concen-
Cr(III) 1428.57 0.0162 0.9545
trations of metal ions, 50 ppm.
R. Say et al. / Applied Clay Science 31 (2006) 298305 303

was studied to adsorption of Pb(II) ions on modified Table 3


pyrophyllite and was reported maximum adsorption of Adsorptiondesorption cycles for heavy metal ions
Pb(II) ions on modified pyrophyllite at pH about 6.5 Cycle Cd(II) Cr(III) Pb(II)
and adsorption time was found to be 90 min (Erdemo- No.
Adsorp Desorp. Adsorp. Desorp. Adsorp. Desorp.
lu et al., 2004). (mg/g) (%) (mg/g) (%) (mg/g) (%)
1 29.1 93.6 22.8 96.1 38.1 91.6
3.2.4. Competitive adsorption 2 28.6 95.1 22.6 98.6 37.8 93.4
Adsorption capacities of dithiocarbamate-anchored 3 28.4 94.7 22.0 96.2 37.6 90.6
4 27.6 92.8 21.8 95.1 37.1 92.7
polymer/organosmectite composites for metal ions
5 26.4 91.3 21.5 94.4 36.7 89.6
under competitive conditions (adsorption from solu-
tions containing all heavy metal ions) for Pb(II), Cd metal on Na-montmorillonite by breakthrough technique.
(II) and Cr(III) are given in Table 2. The competitive The total capacity of Na-montmorillonite towards investi-
adsorption capacities are; 43.6 for Pb(II), 20.7 for Cd(II) gated metals increases in order Pb =Cdb Cu b Zn-
and 11.02 mg g 1 for Cr(III) at 50 ppm initial concen- Mn b Nib Cr (Abollino et al., 2003). Adebowale et al.
tration and 70.4 for Pb(II), 31.8 for Cd(II) and 20.3 mg researched adsorption of some heavy metal-ions on sulfate
g 1 for Cr(III) at 100 ppm initial concentration. and phosphate-modified kaoline and the metal ions
The dithiocarbamate-anchored polymer/organosmec- showed stronger with affinity for the phosphate modified
tite composites exhibit the following metal ion affinity adsorbent with Pb N CuN Zn N Cd (Adebowale et al., 2005).
sequence (weight basis) under competitive adsorption Salih et al. investigated the adsorption of heavy metal ions
conditions: Pb(II) N Cd(II) N Cr(III). But it should be onto dithizone-anchored poly (EDMA-HEMA) beads and
noted that the maximum adsorption capacities (molar reported affinity order under non-competitive and compet-
basis) of the nanocomposites are 210.42 for Pb(II), itive adsorption, i.e Cr(III) N Pb(II)N Hg(II) N Cd(II) (Salih
184.16 for Cd(II) and 211.92 mol g 1 for Cr(III) at et al., 1998). Also in this study, dithiocarbamate-anchored
50 ppm initial concentration and 339.76 for Pb(II), polymer/organosmectite composites exhibit the following
282.91 for Cd(II) and 390.38 mol g 1 for Cr(III) at metal ion affinity sequence under non-competitive and
100 ppm initial concentration. The order of affinity competitive conditions, Cr(III) N Pb(II) N Cd(II).
based on micromole uptake by the sorbent differs
according to weight base and is as follows: Cr(III) N Pb 3.2.5. Reusability of nanocomposites
(II) N Cd(II). To be of use in metal ion recycling prosesses, metal
The removal of Co(II), Cu(II), Zn(II), Cd(II) and Pb(II) ions chelated should be easily desorbed under suitable
single and multicomponent heavy-metal solutions in Mg- conditions. Desorption experiments were performed
enriched sepiolite was investigated and was found the with 0.5 M NaCl as the desorption agent. The dithiocar-
sepiolite sorption efficiency sequence as, for single com- bamate-anchored composites loaded the maximum
ponent solution, Pb b Cdb Co b Zn b Cu, and, for multi- amounts of the respective metal ions when placed within
component solution Pb = Cob Cd b Znb Cu (Brigatti et the desorption medium, the amount of metal ions des-
al., 2000). Abollino et al. studied adsorption of heavy orbed in 60 min was measured. Table 3 shows the
adsorptiondesorption values of heavy metal ions by
Table 2 dithiocarbamate-anchored composites after several
Competitive adsorption of heavy metal ions on the dithiocarbamate- cycles of consecutive adsorption and desorption. This
anchored composites
table clearly shows that the dithiocarbamate-anchored
a b
Ions Concentration of each Concentration of each composites can be used repeatedly without loosing their
metal ions, 50 ppm metal ions, 100 ppm adsorption capacities for all metal ions studied here.
mg mol mg mol
Adsorbed Adsorbed Adsorbed Adsorbed 4. Conclusion
ion g 1 ion g 1 ion g 1 ion g 1
polymer a polymer a polymer b polymer b
The present investigation shows that the dithiocar-
Pb(II) 43.6 210.42 70.4 339.76
bamate-anchored polymer/organosmectite composites
Cd(II) 20.7 184.16 31.8 282.91
Cr(III) 11.02 211.92 20.3 390.38 can be used for adsorption/desorption of Pb(II), Cd
a (II) and Cr(III) ions from aqueous solution under non-
Concentration of each metal ions, 50 ppm; pH 6.0, temperature
20 C.
competitive and competitive conditions. The maximum
b
Concentration of each metal ions, 100 ppm; pH 6.0, temperature desorption capacities of these affinity composites from
20 C. their single metal ions solutions were 170.7 mg g 1
304 R. Say et al. / Applied Clay Science 31 (2006) 298305

(823.84 mol g 1), 82.2 mg g 1 (731.31 mol g 1) and El-Nahhal, Y.Z., Safi, J.M., 2004. Adsorption of phenanthrene on
71.1 mg g 1 (1367.30 mol g 1) for Pb(II), Cd(II) and organoclays from distilled and saline water. J. Colloid Interface
Sci. 269, 265273.
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peted (in case of adsorption from their mixture) the Sayklan, H., 2004. Organo-functional modified pyrophyllite:
amounts of adsorption was 43.6 mg g 1 (210.42 mol preparation, characterisation and Pb(II) ion adsorption property.
g 1) for Pb(II); 20.7 mg g 1 (184.16 mol g 1) for Cd Appl. Clay. Sci. 27, 4152.
(II) and 11.02 mg g 1 (211.92 mol g 1) for Cr(III) at Giannelis, E.P., 1996. Polymer layered silicate nanocomposites. Adv.
Mater. 8 (1), 2935.
50 ppm initial concentration and 70.4 mg g 1 (339.76 Hoins, U., Charlet, L., Sticher, H., 1993. Ligand effect on the
mol g 1) for Pb(II), 31.8 mg g 1 (282.91 mol g 1) adsorption of heavy metals: the sulfate/cadmium/goethite case. Air
for Cd(II) and 20.3 mg g 1 (390.38 mol g 1) for Cr Water Soil Pollut 68, 241255.
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Macromol. Rev. 16, 397522.
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were desorbed successfully by using 0.5 M NaCl as the preconcentration of trace metals. Talanta 37, 491517.
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Acknowledgements E., 2004. Physicochemical studies of cadmium(II) biosorption by
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