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Abstract Superoxide is a reactive oxygen species that is influential in the redox chemistry of a wide range of biological processes and environmental cycles. Using a novel in situ sensor we report the first water column profiles of superoxide in the Baltic Sea, at concentrations higher than previously observed in other oceans. Our data revealed consistent peaks of superoxide (2.0–15.1 nM) in dark waters just below the mixed layer. The oxic waters, low metal concentrations, and lack of sunlight imply that the peak is likely of biological origin. Several profiles displayed a concomitant dip in dissolved oxygen mirroring this superoxide peak, strongly suggesting a link between the two features. The magnitude and distribution of superoxide observed warrants re‐evaluation of the most relevant sources and controls of superoxide in seawater. Locally, these high concentrations of superoxide may create environments conducive to reactions with trace metals and organic matter and present an overlooked sink of oxygen in the Baltic Sea. 

Abstract Marine microbes produce extracellular reactive oxygen species (ROS) such as superoxide and hydrogen peroxide (H₂O₂) as a result of regulated and nonregulated physiological and metabolic reactions. ROS production can be a sink and cryptic recycling flux of dissolved oxygen that may rival other key fluxes in the global oxygen cycle; however, the low abundance and high turnover rate of ROS makes this figure difficult to constrain. One key step in determining the disparity between the gross production of ROS and the net sink of dissolved oxygen lies in understanding the degradation pathways of H₂O₂in the marine water column. In this study, we use isotope‐labeling techniques to determine the redox fate of H₂O₂in a range of marine environments off the West Coast of California. We find that H₂O₂reduction is greater than or equal to H₂O₂oxidation at most sampled depths, with notable exceptions in some surface and intermediate water depths. The observation that H₂O₂oxidation can exceed reduction in the dark ocean indicates the presence of an oxidizing decay pathway that is not among the known suite of microbially mediated enzymatic pathways (i.e., catalase and peroxidase), pointing to an abiotic and/or a nonenzymatic decay pathway at intermediate water depths. These results highlight the complexity and heterogeneity of ROS decay pathways in natural waters and their unconstrained regulation of oxygen levels within the ocean.