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Performance evaluation of two chelating ion-exchange sorbents for the fractionation of labile and inert metal species from aquatic media

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Abstract

The performance of two iminodiacetate chelating resins, applied in an element fractionation scheme, was investigated for the characterization of marine and stream water samples collected in potentially contaminated harbor and industrial zones. The comparison involved an evaluation of the sorption/desorption behavior of Cd, Cu, Pb and Zn on Chelex-100, a sorbent extensively employed for metal speciation studies, and on Lewatit TP-207, a material with similar chelating characteristics for which no applications for fractionation studies are reported. A characterization of the latter resin in terms of the influence of sample pH on the uptake of metals from aqueous solutions and their subsequent acid elution was carried out. Fractionation studies were performed on natural water samples and model solutions resembling their composition, spiked with micromolar concentrations of the metals. The operationally defined fractionation scheme is based on dynamic adsorption of the resin-labile fractions of metals on microcolumns made of the sorbents. This stage is followed by a batch procedure in which the eluent from the column is contacted with fresh resin to discriminate between the relatively stable species unable to react with the resin during the column interaction time, and the strongly complexed metals that do not interact with the sorbent even for periods of several hours. Results were obtained from coarsely filtered sub-samples and from specimens passed through membrane filters of pore size 0.45 and 0.22 µm. The method was also assessed with model solutions of the metals containing variable concentrations (in the 10-3–10-7 molar range) of complex forming agents such as nitrilotriacetic acid and trans-1,2-diaminocyclohexane-N,N,N’,N’-tetraacetic acid. An additional batch method, in which a fixed amount of resin was contacted with sample solution for increasing periods of time and the amount of metal remaining in solution measured as a function of the elapsed time, was used to obtain information on the kinetics of dissociation of species formed in the presence of added complexants. The behavior of both resins was similar, demonstrating that the discrimination of species derived from experiments with Chelex-100 may be properly validated by independent fractionation tests carried out with Lewatit TP-207. The behavior of the sorbents is also discussed in terms of the possible influence of particulate or colloidal materials and of kinetic effects related to the presence of complexing agents.

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Acknowledgements

The authors are indebted to Myriam Crespo (CERZOS, CONICET) for her collaboration in FAAS and ICP OES analyses, to Vivianne Bruyere for calculations with the MINEQL program, and to Raquel T. Gettar and Ana M. La Gamma for valuable comments. The provision of Lewatit TP-207 resin by Bayer Argentina is gratefully acknowledged. This work was carried out as part of the CNEA Program P5, Projects PID-36–2 and 36–4 (CAC). Financial support was also provided by Universidad Nacional del Sur, Bahía Blanca (Projects 24 M 052 and 068).

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Correspondence to Daniel A. Batistoni.

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Alvarez, M.B., Malla, M.E. & Batistoni, D.A. Performance evaluation of two chelating ion-exchange sorbents for the fractionation of labile and inert metal species from aquatic media. Anal Bioanal Chem 378, 438–446 (2004). https://doi.org/10.1007/s00216-003-2237-y

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