Diel Variability of pCO2 and CO2 Outgassing from the Lower Mississippi River: Implications for Riverine CO2 Outgassing Estimation

Carbon dioxide (CO2) outgassing from river surface waters is an important component of the global carbon cycle currently not well constrained. To test the hypothesis that riverine partial pressure of CO2 (pCO(2)) and CO2 outgassing rates differ between daylight and darkness, we conducted in-situ pCO(2) and ambient water measurements over four 24-h periods in the spring and summer of 2018 in the Lower Mississippi River under varying flow regimes. We hypothesized that diel pCO(2) variation will correlate inversely with solar radiation due to light-induced photosynthesis. Despite differing ambient conditions between seasons, we found a consistent diel cycle of riverine pCO(2), with highest values before sunset and lowest values during peak daylight. Recorded pCO(2) measurements varied by 206-607 mu atm in spring and 344-377 mu atm in summer, with significantly lower records during daylight in summer. CO2 outgassing was significantly lower during daylight in both seasons, with diel variation ranging between 1.5-4.4 mmol m(-2) h(-1) in spring and 1.9-2.1 mmol m(-2) h(-1) in summer. Daily outgassing rates calculated incorporating diel variation resulted in significantly greater rates (26.2 +/- std. 12.7 mmol m(-2) d(-1)) than calculations using a single daily pCO(2) value. This study suggests a likely substantial underestimation of carbon outgassed from higher order rivers that make up a majority of the global river water surface. The findings highlight the need for high temporal resolution data and further research on diel CO2 outgassing in different climate regions to constrain uncertainties in riverine flux estimation.