Controls on buffering and coastal acidification in a temperate estuary

Estuaries may be uniquely susceptible to the combined acidification pressures of atmospherically driven ocean acidification (OA), biologically driven CO2 inputs from the estuary itself, and terrestrially derived freshwater inputs. This study utilized continuous measurements of total alkalinity (TA) and the partial pressure of carbon dioxide (pCO(2)) from the mouth of Great Bay, a temperate northeastern U.S. estuary, to examine the potential influences of endmember mixing and biogeochemical transformation upon estuary buffering capacity (beta-H). Observations were collected hourly over 28 months representing all seasons between May 2016 and December 2019. Results indicated that endmember mixing explained most of the observed variability in TA and dissolved inorganic carbon (DIC), concentrations of which varied strongly with season. For much of the year, mixing dictated the relative proportions of salinity-normalized TA and DIC as well, but a fall season shift in these proportions indicated that aerobic respiration was observed, which would decrease beta-H by decreasing TA and increasing DIC. However, fall was also the season of weakest statistical correspondence between salinity and both TA and DIC, as well as the overall highest salinity, TA and beta-H. Potential biogeochemically driven beta-H decreases were overshadowed by increased buffering capacity supplied by coastal ocean water. A simple modeling exercise showed that mixing processes controlled most monthly changes in TA and DIC, obscuring impacts from air-sea exchange or metabolic processes. Advective mixing contributions may be as important as biogeochemically driven changes to observe when evaluating local estuarine and coastal OA.