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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.
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
Q Co CA :V =m: 1
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
(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.
Cr(III), respectively. When the heavy metal ions com- Erdemolu, M., Erdemolu, S., Sayklan, F., Akarsu, M., ener, .,
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.
(III) at 100 ppm initial concentration. The dithiocarba- Kaneko, M., Tsuchida, E., 1981. Formation, characterization, and
mate-anchored composites exhibit the following metal catalytic activities of polymer-metal complexes. J. Polym. Sci.,
Macromol. Rev. 16, 397522.
ion affinity sequence under non-competitive and com- Kantipuly, C., Katragadda, A., Chow, A., Gesser, H.D., 1990.
petitive conditions, Cr(III) N Pb(II) N Cd(II). Metal ions Chelating polymers and related supports for separation and
were desorbed successfully by using 0.5 M NaCl as the preconcentration of trace metals. Talanta 37, 491517.
eluant, therefore it was possible to use the same compo- Konishi, Y., Asai, Midoh, Y., Oku, M., 1993. Recovery of cadmium,
sites in repeated adsorptiondesorption cycles. Consid- andlanthanum by biopolymer gel particles of alginic acid. Sep. Sci.
Technol. 28 (9), 16911702.
ering above results, it can be said that the study Lee, D.C., Jang, L.W., 1996. Preparation and characterization of
explained here is cheap and highly selective method PMMA-Clay hybrid composite by emulsion polymerization. J.
for the removal of heavy metal ions. Appl. Polym. Sci. 61 (7), 11171122.
Loidero, P., Cordero, B., Grille, Z., Herrero, R., Sastre De Vicente, M.
Acknowledgements E., 2004. Physicochemical studies of cadmium(II) biosorption by
the invasive Alha in Europe, Sargassum muticum. Biotechnol.
Bioeng. 88 (2), 237247.
This study was supported by The Scientific and Lothenbach, Furrer, G., Schulin, R., 1997. Immobilization of heavy
Technical Research Council of Turkey (TBTAK- metals by polynuclear aluminium and montmorillonite com-
AYDAG-104Y313). pounds. Environ. Sci. Technol. 31, 14521462.
Malakul, P., Srinivasan, K.R., Wang, H., 1998. Metal adsorption and
desorption characteristics of surfactant-modified clay complexes.
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