The combined effects of anthropogenic and biological CO2 inputs may lead to more rapid acidification in coastal waters compared to the open ocean. It is less clear, however, how redox reactions would contribute to acidification. Here we report estuarine acidification dynamics based on oxygen, hydrogen sulfide (H2S), pH, dissolved inorganic carbon and total alkalinity data from the Chesapeake Bay, where anthropogenic nutrient inputs have led to eutrophication, hypoxia and anoxia, and low pH. We show that a pH minimum occurs in mid-depths where acids are generated as a result of H2S oxidation in waters mixed upward from the anoxic depths. Our analyses also suggest a large synergistic effect from river–ocean mixing, global and local atmospheric CO2 uptake, and CO2 and acid production from respiration and other redox reactions. Together they lead to a poor acid buffering capacity, severe acidification and increased carbonate mineral dissolution in the USA’s largest estuary.

Oceanic uptake of anthropogenic carbon dioxide (CO2) from the atmosphere has changed ocean biogeochemistry and threatened the health of organisms through a process known as ocean acidification (OA). Such large-scale changes affect ecosystem functions and can have effects on societal uses, fisheries resources, and economies. In many large estuaries, anthropogenic CO2-induced acidification is enhanced by strong stratification, long water residence times, eutrophication, and a weak acid–base buffer capacity. In this article, we review how a variety of processes influence aquatic acid–base properties in estuarine waters, including river–ocean mixing, upwelling, air–water gas exchange, biological production and subsequent respiration, anaerobic respiration, calcium carbonate (CaCO3) dissolution, and benthic inputs. We emphasize the spatial and temporal dynamics of partial pressure of CO2 ( pCO2), pH, and calcium carbonate mineral saturation states. Examples from three large estuaries—Chesapeake Bay, the Salish Sea, and Prince William Sound—are used to illustrate how natural and anthropogenic processes and climate change may manifest differently across estuaries, as well as the biological implications of OA on coastal calcifiers. Expected final online publication date for the Annual Review of Marine Science, Volume 13 is January 4, 2021. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Few estuaries have inorganic carbon datasets with sufficient spatial and temporal coverage for identifying acidification baselines, seasonal cycles and trends. The Chesapeake Bay, though one of the most well-studied estuarine systems in the world, is no exception. To date, there have only been observational studies of inorganic carbon distribution and flux in lower bay sub-estuaries. Here, we address this knowledge gap with results from the first complete observational study of inorganic carbon along the main stem. Dissolved inorganic carbon (DIC) and total alkalinity (TA) increased from surface to bottom and north to south over the course of 2016, mainly driven by seasonal changes in river discharge, mixing, and biological carbon dioxide (CO 2 ) removal at the surface and release in the subsurface. Upper, mid-and lower bay DIC and TA ranged from 1000-1300, 1300-1800, and 1700-1900 µmol kg −1 , respectively. The pH range was large, with maximum values of 8.5 at the surface and minimums as low as 7.1 in bottom water in the upper and mid-bay. Seasonally, the upper bay was the most variable for DIC and TA, but pH was more variable in the mid-bay. Our results reveal that low pH is a continuing concern, despite reductions in nutrient inputs. There was active internal recycling of DIC and TA, with a large inorganic carbon removal in the upper bay and at salinities < 5 most months, and a large addition in the mid-salinities. In spring and summer, waters with salinities between 10 and 15 were a large source of DIC, likely due to remineralization of organic matter and dissolution of CaCO 3 . We estimate that the estuarine export flux of DIC and TA in 2016 was 40.3 ± 8.2 × 10 9 mol yr −1 and 47.1 ± 8.6 × 10 9 mol yr −1 . The estuary was likely a large sink of DIC, and possibly a weak source of TA. These results support the argument that the Chesapeake Bay may be an exception to the long-standing assumption that estuaries are heterotrophic. Furthermore, they underline the importance of large estuarine systems for mitigating acidification in coastal ecosystems, since riverine chemistry is substantially modified within the estuary.