Sampling and analysing mixtures of sulphate, sulphite, thiosulphate and polythionate.

Interpreting the redox chemistry of sulphur in aqueous systems requires the analysis of mixtures of various sulphoxy anions. Previous methods have been too involved to permit high sample throughout if good quality control is to be maintained. Methods based on ion chromatography have been developed for the direct determination of SO(2-)(4), SO(2-)(3), S(2)O(2-)(3), and SCN(-). The determination of thiocyanate permits the indirect determination of polythionates by treatment with cyanide. Formate, acetate, F(-), Cl(-), CO(2-)(3), and PO(3-)(4), do not interfere, but NO(-)(2) and NO(-)(3) interfere with determination of SO(2-)(3),. The sample preservation treatment includes addition of formaldehyde, cation-exchange and cold storage, to retard oxidation of S(2)O(2-)(3), and SO(2-)(3), and inhibits the rearrangement of SO(2-)(3),/S(2)O(2-)(3),/S(n)O(2-)(6), mixtures caused by bimolecular nucleophilic displacement (S(N)2) reactions. Treated samples may be stored for up to 6 weeks with only minor loss of thiosulphate.