Carbonate buffering and metabolic controls on carbon dioxide in rivers

Multiple processes support the significant efflux of carbon dioxide (CO 2 ) from rivers and streams. Attribution of CO 2 oversaturation will lead to better quantification of the freshwater carbon cycle and provide insights into the net cycling of nutrients and pollutants. CO 2 production is closely related to O 2 consumption because of the metabolic linkage of these gases. However, this relationship can be weakened due to dissolved inorganic carbon inputs from groundwater, carbonate buffering, calcification, and anaerobic metabolism. CO 2 and O 2 concentrations and other water quality parameters were analyzed in two data sets: a synoptic field study and nationwide water quality monitoring data. CO 2 and O 2 concentrations were strongly negatively correlated in both data sets ( ρ  = −0.67 and ρ  = −0.63, respectively), although the correlations were weaker in high‐alkalinity environments. In nearly all samples, the molar oversaturation of CO 2 was a larger magnitude than molar O 2 undersaturation. We used a dynamically coupled O 2 CO 2 model to show that lags in CO 2 air‐water equilibration are a likely cause of this phenomenon. Lags in CO 2 equilibration also impart landscape‐scale differences in the behavior of CO 2 between high‐ and low‐alkalinity watersheds. Although the concept of carbonate buffering and how it creates lags in CO 2 equilibration with the atmosphere is well understood, it has not been sufficiently integrated into our understanding of CO 2 dynamics in freshwaters. We argue that the consideration of carbonate equilibria and its effects on CO 2 dynamics are primary steps in understanding the sources and magnitude of CO 2 oversaturation in rivers and streams.