Description: Estuaries regulate carbon cycling along the land-ocean continuum and thus influence carbon export to the ocean, and global carbon budgets. The Elbe Estuary in Germany has been altered by large anthropogenic perturbations, such as widespread heavy metal pollution, minimally treated wastewater before the 1980s, establishment of wastewater treatment plants after the 1990s, and an overall nutrient and pollutant load reduction in the last three decades. Based on an extensive evaluation of key ecosystem variables, and an analysis of the available inorganic and organic carbon records, this study has identified three ecosystem states in recent history: the polluted (1985–1990), transitional (1991–1996), and recovery (1997–2018) states. The polluted state was characterized by very high dissolved inorganic carbon (DIC) and ammonium concentrations, toxic heavy metal levels, dissolved oxygen undersaturation, and low pH. During the transitional state, heavy metal pollution decreased by 〉 50%, and primary production re-established in spring to summer, with weak seasonality in DIC. Since 1997, during the recovery state, DIC seasonality was driven by primary production, and DIC significantly increased by 〉 23 μmol L−1 yr−1 in the mid to lower estuary, indicating that, along with the improvement in water quality the ecosystem state is still changing. Large anthropogenic perturbations can therefore alter estuarine ecosystems (on the order of decades), as well as induce large and complex biogeochemical shifts and significant changes to carbon cycling.

Description: Estuaries are an important contributor to the global carbon budget, facilitating carbon removal, transfer, and transformation between land and the coastal ocean. Estuaries are susceptible to global climate change and anthropogenic perturbations. We find that a long-term significant mid-estuary increase in dissolved inorganic carbon (DIC) of 6–21 µmol kg−1 yr−1 (1997–2020) in a temperate estuary in Germany (Elbe Estuary) was driven by an increase in upper-estuary particulate organic carbon (POC) content of 8–14 µmol kg−1 yr−1. The temporal POC increase was due to an overall improvement in water quality observed in the form of high rates of primary production and a significant drop in biological oxygen demand. The magnitude of mid-estuary DIC gain was equivalent to the increased POC production in the upper estuary, suggesting that POC is effectively remineralized and retained as DIC in the mid-estuary, with the estuary acting as an efficient natural filter for POC. In the context of this significant long-term DIC increase, a recent extended drought period (2014–2020) significantly lowered the annual mean river discharge (468 ± 234 m3 s−1) compared to the long-term mean (690 ± 441 m3 s−1, 1960–2020), while the late spring internal DIC load in the estuary doubled. The drought induced a longer dry season, starting in May (earlier than normal), increased the residence time in the estuary and allowed for a more complete remineralization period of POC. Annually, 77 %–94 % of the total DIC export was laterally transported to the coastal waters, reaching 89 ± 4.8 Gmol C yr−1, and thus, between 1997 and 2020, only an estimated maximum of 23 % (10 Gmol C yr−1) was released via carbon dioxide (CO2) evasion. Export of DIC to coastal waters decreased significantly during the drought, on average by 24 % (2014–2020: 38 ± 5.4 Gmol C yr−1), compared to the non-drought period. In contrast, there was no change in the water–air CO2 flux during the drought. We have identified that seasonal changes in DIC processing in an estuary require consideration when estimating both the long-term and future changes in water–air CO2 flux and DIC export to coastal waters. Regional and global carbon budgets should therefore take into account carbon cycling estimates in estuaries, as well as their changes over time in relation to impacts of water quality changes and extreme hydrological events.