Abstract:
In this study, the concentration and isotopic composition of dissolved organic carbon (DOC) and dissolved inorganic carbon (DIC) are measured in the karst groundwater of the Otter Creek watershed of the Cumberland Plateau of Kentucky, USA. Comparisons among these data and with the geochemistry of carbonate and gypsum equilibrium reactions reveal that DOC concentration is inversely related to discharge, multiple reaction pathways provide DIC with isotopic enrichment that may be directly related to mineral saturation, and oxidation of reduced sulfur is possible for dissolution. DOC is derived from C3 vegetation with an average δ13C DOC of ‒27‰. DIC in groundwater is derived from both pedogenic CO2  and HCO3 - from dissolved carbonate. At input sites to the karst aquifers DIC concentrations are expectedly low, less than 1 mmol/L, in waters that are undersaturated with respect to calcite. At the output of these karst aquifers DIC concentrations reach 3 mmol/L in waters that are at or above calcite saturation. Values of δ13C DIC range between ‒6.3 and ‒12.4‰ with CO2 degassing and calcite precipitation at some sites obfuscating a simple relationship between δ13C DIC, discharge, and mineral saturation. In addition, concentrations of DIC in sulfur seeps within the watershed range between 2–7 mmol/L with δ13C DIC values in some samples skewed more toward the anticipated value of carbonate bedrock than would be expected from reactions with carbonic acid alone. This suggests that the oxidation of reduced sulfur from shallow oilfield brines liberates bedrock DIC through reactions with sulfuric acid.