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The carbonate chemistry was investigated in the semiarid eutrophic Araruama Lagoon (Brazil), one of the largest hypersaline coastal lagoons in the world. Spatial surveys during winter and summer periods were performed, in addition to a diurnal sampling in summer. The hypersaline waters have higher concentrations of total alkalinity (TA) and dissolved inorganic carbon (DIC) than the seawater that feed the lagoon, due to evaporation. However, TA and DIC concentrations were lower than those expected from evaporation. Calcium carbonate (CaCO3) precipitation partially explained these deficits. The negative correlation between the partial pressure of CO2 (pCO2) and chlorophyll a (Chl a) indicated that DIC was also consumed by primary producers. The uptake by photosynthesis contributes to 57–63% of DIC deviation from evaporation, the remaining credited to CaCO3 precipitation. Marked pCO2 undersaturation was prevalent at the innermost region with shallow, confined, and phytoplankton-dominated waters, with a strong enrichment of heavier carbon isotope (δ13C-DIC up to 5.55‰), and highest pH (locally counter-acting the process of ocean acidification). Oversaturation was restricted to an urbanized region, and during night-time. The lagoon behaved as a marked CO2 sink during winter (− 15.32 to − 10.15 mmolC m−2 day−1), a moderate sink during summer (− 5.50 to − 4.67 mmolC m−2 day−1), with a net community production (NCP) of 93.7 mmolC m−2 day−1 and prevalence of net autotrophic metabolism. A decoupling between CO2 and O2 exchange rate at the air–water interface was attributed to differences in gas solubility, and high buffering capacity. The carbonate chemistry reveals simultaneous and antagonistic actions of CaCO3 precipitation and autotrophic metabolism on CO2 fluxes, and could reflect future conditions in populated and semiarid coastal ecosystems worldwide. [ABSTRACT FROM AUTHOR]

Increasing eutrophication of coastal waters generates disturbances in greenhouse gas (GHG) concentrations and emissions to the atmosphere that are still poorly documented, particularly in the tropics. Here, we investigated the concentrations and diffusive fluxes of carbon dioxide (CO2) and methane (CH4) in the urban-dominated Jacarepagua Lagoon Complex (JLC) in Southeastern Brazil. This lagoonal complex receives highly polluted freshwater and shows frequent occurrences of anoxia and hypoxia and dense phytoplankton blooms. Between 2017 and 2018, four spatial surveys were performed (dry and wet conditions), with sampling in the river waters that drain the urban watershed and in the lagoon waters with increasing salinities. Strong oxygen depletion was found in the rivers, associated with extremely high values of partial pressure of CO2 (pCO2; up to 20,417 ppmv) and CH4 concentrations (up to 288,572 nmol L−1). These high GHG concentrations are attributed to organic matter degradation from untreated domestic effluents mediated by aerobic and anaerobic processes, with concomitant production of total alkalinity (TA) and dissolved inorganic carbon (DIC). In the lagoon, GHG concentrations decreased mainly due to dilution with seawater and degassing. In addition, the phytoplankton growth and CH4 oxidation apparently consumed some CO2 and CH4, respectively. TA concentrations showed a marked minimum at salinity of ~20 compared to the two freshwater and marine end members, indicating processes of re-oxidation of inorganic reduced species from the low-salinity region, such as ammonia, iron, and/or sulfides. Diffusive emissions of gases from the entire lagoon ranged from 22 to 48 mmol C m−2 d−1 for CO2 and from 2.2 to 16.5 mmol C m−2 d−1 for CH4. This later value is among the highest documented in coastal waters. In terms of global warming potential (GWP) and CO2 equivalent emissions (CO2-eq), the diffusive emissions of CH4 were higher than those of CO2. These results highlight that highly polluted coastal ecosystems are hotspots of GHG emissions to the atmosphere, which may become increasingly significant in future global carbon budgets. [ABSTRACT FROM AUTHOR]

Increasing eutrophication of coastal waters generates disturbances in greenhouse gas (GHG) concentrations and emissions to the atmosphere that are still poorly documented, particularly in the tropics. Here, we investigated the concentrations and diffusive fluxes of carbon dioxide (CO 2 ) and methane (CH 4 ) in the urban-dominated Jacarepagua Lagoon Complex (JLC) in Southeastern Brazil. This lagoonal complex receives highly polluted freshwater and shows frequent occurrences of anoxia and hypoxia and dense phytoplankton blooms. Between 2017 and 2018, four spatial surveys were performed (dry and wet conditions), with sampling in the river waters that drain the urban watershed and in the lagoon waters with increasing salinities. Strong oxygen depletion was found in the rivers, associated with extremely high values of partial pressure of CO 2 (pCO 2 ; up to 20,417 ppmv) and CH 4 concentrations (up to 288,572 nmol L -1 ). These high GHG concentrations are attributed to organic matter degradation from untreated domestic effluents mediated by aerobic and anaerobic processes, with concomitant production of total alkalinity (TA) and dissolved inorganic carbon (DIC). In the lagoon, GHG concentrations decreased mainly due to dilution with seawater and degassing. In addition, the phytoplankton growth and CH 4 oxidation apparently consumed some CO 2 and CH 4 , respectively. TA concentrations showed a marked minimum at salinity of ~20 compared to the two freshwater and marine end members, indicating processes of re-oxidation of inorganic reduced species from the low-salinity region, such as ammonia, iron, and/or sulfides. Diffusive emissions of gases from the entire lagoon ranged from 22 to 48 mmol C m -2 d -1 for CO 2 and from 2.2 to 16.5 mmol C m -2 d -1 for CH 4 . This later value is among the highest documented in coastal waters. In terms of global warming potential (GWP) and CO 2 equivalent emissions (CO 2 -eq), the diffusive emissions of CH 4 were higher than those of CO 2 . These results highlight that highly polluted coastal ecosystems are hotspots of GHG emissions to the atmosphere, which may become increasingly significant in future global carbon budgets., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)