Sulfur-oxygen isotope analysis of SO42− sources in cave dripwater and their influence on the karst carbon cycle

Sulfuric acid is involved in carbonate rock dissolution in karst areas and affects regional hydrogeochemical and carbon cycling processes. Sulfate sources and carbonate weathering at dripwater points of different hydrological types also differ significantly. Therefore, in this paper, three dripwater points (SQ2#, PB and MH6#) of different hydrological types in Dafeng Cave and Mahuang Cave were selected and systematically analyzed. The results show that: (1) ions in the cave dripwater mainly originated from rock weathering, and the water chemistry types were HCO3·Ca-Mg and HCO3-SO4·Ca-Mg. (2) Sulfur and oxygen isotopes reveal that sulfate in the cave water of Shuanghe Cave mainly came from a mixture of soil sulfate and chemical fertilizers. (3) The Simmr model shows that the main sources of sulfate at each dripwater point were natural sources, such as soil sulfate and gypsum dissolution. The natural sources contributed more than 80% of the sulfate in the cave water and were less affected by anthropogenic activities. (4) Carbonate weathering by sulfuric acid (CSW) can accelerate rock weathering and the prior calcite precipitation effect, involving regional CO2 exchange through fissure pipes. The forward model results show that CSW reduced the karst carbon sinks at SQ2#, PB and MH6# by about 19.44%, 23.88% and 12.74%, respectively. Therefore, the impact cannot be ignored in assessing carbon source and sink processes in karst areas.