Dynamics of inorganic carbon and pH in a large subtropical continental shelf system: Interaction between eutrophication, hypoxia, and ocean acidification

We examined the dynamics of dissolved inorganic carbon (DIC) and pH in the Pearl River Estuary (PRE) and the adjacent northern South China Sea (NSCS) shelf in summer, aiming for a better understanding of the interaction between eutrophication, hypoxia, and ocean acidification. Using a semi-analytical diagnostic approach based on validated multiple end-member water mass mixing models, we showed a −191 ± 54 μmol kg−1 deficit in DIC concentrations in an extensive surface plume bulge, corresponding to a significant pH increase of ∼ 0.57 ± 0.19 units relative to conservative mixing. In contrast, DIC additions in the bottom hypoxic zone reached ∼ 139 ± 21 μmol kg−1, accompanied by a decrease in pH of −0.30 ± 0.04 units. In combination with stable carbon isotopic compositions, we found biological production and CO₂ outgassing to be responsible for DIC deficits in surface waters, while degradation of organic matter (OM) accounted for DIC additions in bottom waters. The PRE-NSCS plume system as a whole served as a net source of atmospheric CO₂ from the perspective of Lagrangian observations, because strong CO₂ outgassing in the inner estuary overwhelmed the CO₂ uptake in the plume despite strong phytoplankton blooms. Using a two-layer box model, we further estimated that at least ∼ 45 ± 13% of eutrophication-driven OM production in the surface plume accounted for 67 ± 18% of the DIC addition and oxygen consumption in bottom waters. Eutrophication also buffered ocean acidification in surface waters while hypoxia enhanced it in bottom waters, but their effects on acid-base buffering capacity were secondary to the amplification of coastal ocean acidification caused by freshwater inputs.