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Distinct concentration‐discharge dynamics in temperate streams and rivers: CO2 exhibits chemostasis while CH4 exhibits source limitation due to temperature control

Streams and rivers are significant sources of carbon dioxide (CO2) and methane (CH4) to the atmosphere. However, the magnitudes of these fluxes are uncertain, in part, because dissolved greenhouse gases (GHGs) can exhibit high spatiotemporal variability. Concentration‐discharge (C‐Q) relationships are commonly used to describe temporal variability stemming from hydrologic controls on solute production and transport. This study assesses how the partial pressures of two GHGs—pCO2 and pCH4—vary across hydrologic conditions over 4 yr in eight nested streams and rivers, at both annual and seasonal timescales. Overall, the range of pCO2 was constrained, ranging from undersaturated to nine times oversaturated, while pCH4 was highly variable, ranging from 3 to 500 times oversaturated. We show that pCO2 exhibited chemostatic behavior (i.e., no change with Q), in part, due to carbonate buffering and seasonally specific storm responses. In contrast, we show that pCH4 generally exhibited source limitation (i.e., a negative relationship with Q), which we attribute to temperature‐mediated production. However, pCH4 exhibited chemostasis in a wetland‐draining stream, likely due to hydrologic connection to the CH4‐rich wetland. These findings have implications for CO2 and CH4 fluxes, which are controlled by concentrations and gas transfer velocities. At high Q, enhanced gas transfer velocity acts on a relatively constant CO2 stock but on a diminishing CH4 stock. In other words, CO2 fluxes increase with Q, while CH4 fluxes are modulated by the divergent Q dynamics of gas transfer velocity and concentration.