Matthew J Winnick, Brian Saccardi

Rivers and streams play an important role within the global carbon cycle, in part through emissions of CO2 to the atmosphere. However, the sources of this CO2 and their spatiotemporal variability are difficult to constrain. Recent work has highlighted the role of carbonate buffering reactions that may serve as a source of CO2 in high alkalinity systems. In this study, we seek to develop a quantitative framework for the role of carbonate buffering in the fluxes and spatiotemporal patterns of CO2 and the stable and radio- isotope composition of dissolved inorganic carbon (DIC). We incorporate DIC speciation calculations of carbon isotopologues into a stream network CO2 model and perform a series of experiments, ranging from the degassing of a groundwater seep to the simulation of 5th-order stream network. We find that carbonate buffering reactions contribute >60% of emissions in high-alkalinity, moderate GW-pCO2 environments that may characterize carbonate bedrock systems. However, atmosphere equilibration timescales of pCO2 are minimally affected, which contradicts hypotheses that carbonate buffering maintains high pCO2 across Strahler orders in high alkalinity systems. In contrast, alkalinity dramatically increases isotope equilibration timescales, which significantly complicates isotopic methods of CO2 source partitioning by decoupling pCO2 from isotopic composition even under low alkalinity. Based on similar impacts on atmospheric equilibration for stable and radio- carbon isotopologues, we develop a quantitative method for distinguishing groundwater from stream corridor CO2 sources in carbonate-dominated watersheds. Together, these results provide a framework to guide fieldwork and interpretations of stream network CO2 patterns across variable alkalinities.