Rapid and Sensitive Analytical Method for Monitoring of 12 Organotin Compounds in Natural Waters

A rapid analytical method for the simultaneous determination of 12 different organotin compounds (OTC): methyl-, butyl-, phenyl- and octyl-tins in natural water samples was developed. It comprises of in situ derivatisation (by using NaBEt4) of OTC in salty or fresh water sample matrix adjusted to pH 6 with Tris-citrate buffer, extraction of ethylated OTC into hexane, separation of OTC in organic phase on 15 m GC column and subsequent quantitative determination of separated OTC by ICP-MS. To optimise the pH of ethylation, phosphate, carbonate and Tris-citrate buffer were investigated alternatively to commonly applied sodium acetate – acetic acid buffer. The ethylation yields in Tris-citrate buffer were found to be better for TBT, MOcT and DOcT in comparison to commonly used acetate buffer. Iso-octane and hexane were examined as organic phase for extraction of ethylated OTC. The advantage of hexane was in its ability for quantitative determination of TMeT. GC column of 15 m in length was used for separation of studied OTC under the optimized separation conditions and its performances compared to 30 m column. The analytical method developed enables sensitive simultaneous determination of 12 different OTC and appreciably shortened analysis time in larger series of water samples. LOD’s obtained for the newly developed method ranged from 0.05–0.06 ng Sn L–1 for methyl-, 0.11–0.45 ng Sn L–1 for butyl-, 0.11–0.16 ng Sn L–1 for phenyl-, and 0.07–0.10 ng Sn L–1 for octyl-tins. By applying the developed analytical method, marine water samples from the Northern Adriatic Sea containing mainly butyl- and methyl-tin species were analysed to confirm the proposed method’s applicability.