Isotopic evidence for determining the sources of dissolved organic sulfur in a forested catchment.

Understanding sulfur (S) biogeochemistry, especially in those watersheds subject to elevated levels of atmospheric S inputs, is needed for determining the factors that contribute to acidification, nutrient losses and the mobilization of toxic solutes (e.g., monomeric aluminum and methylmercury). S is found in a variety of both organic and inorganic forms undergoing a range of biotic and abiotic transformations. In watersheds with decreasing atmospheric S inputs, internal cycling is becoming dominant in affecting whether there is net loss or retention of S. Little attention has been given to the role of dissolved organic S (DOS) in affecting S biogeochemistry. DOS originates from assimilatory and bacterial dissimilatory S reduction (BDSR), the latter of which produces (34)S-depleted S. Within groundwater of the Archer Creek Catchment in the Adirondack Mountains (New York) there was reoxidation of reduced S, which was an important source of SO4(2-). DOS in surface waters had a higher variation of δ(34)S-DOS values (-6.0 to +8.4‰) than inorganic S with δ(34)S-SO4(2-) values ranging from +1.0 to +5.8‰. Inverse correlations between δ(34)S values of SO4(2-) and DOS suggested that BDSR played an important role in producing DOS.

Comparison of sample preparation methods for stable isotope analysis of dissolved sulphate in forested watersheds.

Pretreatment methods for measuring stable sulphur (δ(34)S) and oxygen (δ(18)O) isotope ratios of dissolved sulphate from watersheds have evolved throughout the last few decades. The current study evaluated if there are differences in the measured stable S and O isotope values of dissolved sulphate from forested watersheds when pretreated using three different methods: Method 1 (M1): adsorb sulphate on anion exchange resins and send directly to isotope facility; Method 2 (M2): adsorb sulphate on anion exchange resins, extract sulphate from anion exchange resins, and send the produced BaSO(4) to the isotope facility; and Method 3 (M3): directly precipitate BaSO(4) without anion exchange resins with the precipitates being sent to the isotope facility. We found an excellent agreement of the δ(34)S(sulphate) values among all the three methods. However, some differences were observed in the δ(18)O(sulphate) values (M1 versus M2:-1.5 ‰; M1 versus M3:-1.2 ‰) associated with possible O contamination before isotope measurement. Several approaches are recommended to improve the pretreatment procedures for δ(18)O(sulphate) analysis.