Determination of inorganic sulphur speciation with polarographic techniques: Some preliminary results for recent hypersaline anoxic sediments

Abstract

Polarographic techniques have been used to determine reduced inorganic sulphur speciation in recent anoxic marine sediments from two hypersaline basins, the Tyro and the Bannock Basins, in the Eastern Mediterranean. The following phases were determined: acid volatile sulphur (AVS), pyritic sulphur and zerovalent sulphur. The determination of AVS and pyrite was based respectively on the acidification and Cr(II) reduction of these sulphur components to H 2S. H 2S was collected in base and the sulphide concentration was measured by polarography. Standard Na 2S and pyrite gave recoveries of 99.6% ± 3.9% and 97% ± 12% respectively. Total zerovalent sulphur in a sediment sample was measured by the reaction of sulphite with thiosulphate. Thiosulphate was measured directly by polarography. Pyrite is the main phase of inorganic reduced sulphur in the sediments from the Tyro and the Bannock Basins, and it has about the same average level (125 υmoles per gramme dry weight) in the cores recovered from the two areas. However, the distribution of pyrite in the top 100 cm of the two cores differs significantly. In the Bannock Basin a sharp increase is observed with depth, whereas in the Tyro Basin there is a small decrease with depth. The total amount of reduced inorganic sulphur is less than the total amount of sulphur in the sediments. This indicates that there must be additional sulphur-bearing phases. One of these phases may be gypsum, and indeed, gypsum crystals have been observed in the Bannock Basin. In neither basin is there a significant correlation between reduced sulphur and organic carbon. The pyrite that occurs in these basins may have been formed syngenetically at the interface of the anoxic brine and oxic seawater. Diagenetic pyrite may have been formed within the sediments of the basins. AVS and total zerovalent sulphur are still observed at depth. We therefore suggest that this may be due to the incomplete transformation of AVS and zerovalent sulphur into pyrite.