P. Svete, R. Milačič, B. Mitrović, B. Pihlar
The Royal Society of Chemistry 2001, Analyst, 2001, 126, 1346–1354
Analytical procedures were developed for the speciation of Zn using fast protein liquid chromatography (FPLC), flame atomic absorption spectrometry (FAAS) and convective interaction media (CIM) fast monolithic chromatography with FAAS and electrospray (ES)-MS-MS detection. The investigation was performed on synthetic solutions (2 µg cm-3 Zn) of hydrated Zn2+ species and Zn complexes with citrate, oxalate and EDTA (ligand-to-Zn molar ratio 100 : 1) over a pH range from 5.4 to 7.4. It was found that Zn interacts with various buffers and the careful adjustment of the pH with diluted solutions of KOH is, therefore, required. FPLC separations were carried out on a Mono Q HR 5/5 strong anion-exchange column, applying an aqueous 1 mol dm-3 NH4NO3 linear gradient elution over 15 min, at a flow rate of 1.0 cm3 min−1. The separated Zn species were determined in 1.0 cm3 eluate fractions “off line” by FAAS. Speciation of Zn was also performed on a weak anion-exchange CIM DEAE fast monolithic disc by applying an aqueous 0.4 mol dm-3 NH4NO3 linear gradient elution over 7.5 min, at a flow rate of 2.0 cm3 min−1 and determination of the separated Zn species in 1.0 cm3 eluate fractions “off line” by FAAS. Zn-binding ligands in separated fractions were also characterized by electrospray (ES)-MS-MS analysis. The CIM DEAE disc was found to be more efficient in the separation of negatively charged Zn complexes than the Mono Q FPLC column. On the CIM DEAE disc Zn–citrate was separated from both Zn–oxalate and from Zn–EDTA. All these species were also separated from hydrated Zn2+, which was eluted with the solvent front. This method has an advantage over commonly used analytical techniques for the speciation of Zn which are only able to distinguish between labile and strong Zn complexes. Good repeatability of the measurements (RSD 2–4%), tested for six parallel determinations (2 µg cm-3 Zn) of Zn–EDTA, Zn–citrate and Zn–oxalate was found at a pH of 6.4 on a CIM DAEA disc. The limit of detection (3s) for the separated Zn species was 10 ng cm-3. The proposed analytical procedure was applied to the speciation of Zn in aqueous soil extracts and industrial waste water from a lead and zinc mining area.
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