Sulfate sources constrained by sulfur and oxygen isotopic compositions in the upper reaches of the Xijiang River,China

While it is critical to accurately understand the sources and transformation of sulfate based on time-series analysis, there are limited studies on temporal variation of sulfate in rivers and on rock weathering by sulfuric acids.We conducted a monthly sampling campaign in the Beipan, Nanpan, and Hongshui Rivers over the course of one hydrological year. This study examined seasonal variations in riverine sulfate impacted by the monsoon climate in the upper reaches of the Xijiang River basin. In general, the SO_4~(2-) contents in these rivers dropped from relatively high levels to low values during the high-flow season, in response to increasing discharge. The sulfate was generally enriched in heavy isotopes during the low-flow season compared to the high-flow season. The calculated results indicate that the riverine sulfate was mainly derived from sulfide oxidation, but that evaporite dissolution could be an important source during the low-flow season, based on isotopic evidence. Mine drainage is likely an important source of sulfate to these rivers during the high-flow season due to contributions from fast surface flow, which responds to frequent heavy rain in monsoonal climate regions. Arelatively high proportion of HCO_3~- was found to be derived from rock weathering by sulfuric acid during the high-flow season when compared to that observed during the low-flow season. The results suggest that approximately one quarter of the HCO_3~- in the Hongshui River originated from carbonate weathering by sulfuric acid derived from the oxidation of sulfide. Such information on the specific dual isotopic characteristics of riverine sulfate throughout a hydrological year can provide unique evidence for understanding the temporal variability of sulfate concentrations and weathering processes in rivers.