Abstract
Measurements of riverine dissolved inorganic carbon (DIC), total
alkalinity (AT), pH, and the partial pressure of carbon dioxide (pCO2)
can provide insights into the biogeochemical function of rivers
including the processes that control biological production, chemical
speciation, and air-water CO2 fluxes. The complexity created by these
combined processes dictates that studies of inorganic carbon be made
over broad spatial and temporal scales. Time-series data like these are
relatively rare, however, because sampling and measurements are labor
intensive and, for some variables, good measurement quality is difficult
to achieve (e.g., pH). In this study, spectrophotometric pH and total
alkalinity (AT) were quantified with high precision and accuracy at
biweekly to monthly intervals over a four year period (2018-2021) along
216 km of the Upper Clark Fork River (UCFR) in the northern Rocky
Mountains, USA. We use these and other time-series data to provide
insights into the processes that control river inorganic carbon, with a
focus on pCO2 and air-water CO2 fluxes. We found that seasonal snowmelt
runoff increased pCO2 and that expected increase and decrease of pCO2due
to seasonal heating and cooling were likely offset by an increase and
loss of algal biomass, respectively. Overall, the UCFR was a small net
source (0.08 ± 0.14 mol m-2 d-1) of CO2 to the atmosphere for all four
years of our study with highly variable annual averages. The highly
dynamic, seasonally correlated, offsetting mechanisms highlight the
challenges in predicting pCO2 and air-water CO2 fluxes in rivers.