Seasonal and event variations in δ³⁴S values of stream sulfate in a Vermont forested catchment: Implications for sulfur sources and cycling

Stable sulfur (S) isotope ratios can be used to identify the sources of sulfate contributing to streamwater. We collected weekly and high-flow stream samples for S isotopic analysis of sulfate through the entire water year 2003 plus the snowmelt period of 2004. The study area was the 41-ha forested W-9 catchment at Sleepers River Research Watershed, Vermont, a site known to produce sulfate from weathering of sulfide minerals in the bedrock. The δ³⁴S values of streamwater sulfate followed an annual sinusoidal pattern ranging from about 6.5‰ in early spring to about 10‰ in early fall. During high-flow events, δ³⁴S values typically decreased by 1 to 3‰ from the prevailing seasonal value. The isotopic evidence suggests that stream sulfate concentrations are controlled by: (1) an overall dominance of bedrock-derived sulfate (δ³⁴S ~ 6–14‰); (2) contributions of pedogenic sulfate (δ³⁴S ~ 5–6‰) during snowmelt and storms with progressively diminishing contributions during base flow recession; and (3) minor effects of dissimilatory bacterial sulfate reduction and subsequent reoxidation of sulfides. Bedrock should not be overlooked as a source of S in catchment sulfate budgets.