Sulphur isotopic investigation of a polluted raised bog and the uptake of pollutant sulphur by Sphagnum

The sulphur content and sulphur isotopic composition of Sphagnum as well as anionic compositions and sulphur isotope ratios of rainwater inputs and bog waters have been measured at Thorne Moors, a raised bog in eastern England. Rainwater sulphate isotopic composition shows the sulphur input at this site to be dominated by anthropogenic pollution from fossil fuel burning. Strong depletion of sulphate (low SO2−4/Cl−) and enrichment in 34S in sulphate occurs at depth in the bog porewaters due to bacterial sulphate reduction. Some surface waters have low SO2−4/Cl− and are 34S enriched due to removal of sulphate by downward diffusion into a sulphate-reducing zone. Other sites have high SO2−4/Cl− which appears to result from oxidation of organically bound sulphur in the peat. Sulphur is present in Sphagnum at around 0.2% by weight and is depleted by 0 to -9‰ in the heavier 34S isotope compared to sulphate. Comparison with similar data from pristine coastal sites shows that sulphur incorporation into Sphagnum is enhanced in the polluted site (as Sphagnum sulphur concentrations are higher at lower total sulphur inputs) and that sulphur incorporation is accompanied by a smaller isotopic shift than in the pristine sites. The data support a model of preferential incorporation of partially reduced sulphur species (probably HSO−3) into Sphagnum. In pristine sites these are only available as oxidation products of sulphide formed by sulphate reduction and are 32S depleted. In polluted sites this source is augmented by sulphur(IV) species in atmospheric inputs and the resultant mixture is less depleted in 32S. Thus, in the polluted sites more HSO−3 is available for uptake and the isotopic shift between Sphagnum and aqueous sulphur species is smaller.