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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 A striking feature of Oxygen Deficient Zones (ODZs) on the eastern boundary of the Pacific Ocean are large subsurface plumes of iodide. Throughout the oceans, iodate is the predominant and thermodynamically favored species of dissolved iodine, but iodate is depleted within these plumes. The origin of iodide plumes and mechanism of reduction of iodate to iodide remains unclear but is thought to arise from a combination of in situ reduction and inputs from reducing shelf sediments. To distinguish between these sources, we investigated iodine redox speciation along the Oregon continental shelf. This upwelling system resembles ODZs but exhibits episodic hypoxia, rather than a persistently denitrifying water column. We observed elevated iodide in the benthic boundary layer overlying shelf sediments, but to a much smaller extent than within ODZs. There was no evidence of offshore plumes of iodide or increases in total dissolved iodine. Results suggest that an anaerobic water column dominated by denitrification, such as in ODZs, is required for iodate reduction. However, re‐analysis of iodine redox data from previous ODZ work suggests that most iodate reduction occurs in sediments, not the water column, and is also decoupled from denitrification. The underlying differences between these regimes have yet to be resolved, but could indicate a role for reduced sulfur in iodate reduction if the sulfate reduction zone is closer to the sediment‐water interface in ODZ shelf sediments than in Oregon sediments. Iodate reduction is not a simple function of oxygen depletion, which has important implications for its application as a paleoredox tracer. 

Low oxygen conditions in the modern Baltic Sea are exacerbated by human activities; however, anoxic conditions also prevailed naturally over the Holocene. Few studies have characterized the specific paleoredox conditions (manganous, ferruginous, euxinic) and their frequency in southern Baltic sub-basins during these ancient events. Here, we apply a suite of isotope systems (Fe, Mo, S) and associated elemental proxies (e.g., Fe speciation, Mn) to specifically define water column redox regimes through the Baltic Holocene in a sill-proximal to sill-distal transect (Lille Belt, Bornholm Basin, Landsort Deep) using samples collected during the Integrated Ocean Drilling Program Expedition 347. At the sill-proximal Lille Belt, there is evidence for anoxic manganous/ferruginous conditions for most of the cored interval following the transition from the Ancylus Lake to Littorina Sea but with no clear excursion to more reducing or euxinic conditions associated with the Holocene Thermal Maximum (HTM) or Medieval Climate Anomaly (MCA) events. At the sill-distal southern sub-basin, Bornholm Basin, a combination of Fe speciation, pore water Fe, and solid phase Mo concentration and isotope data point to manganous/ferruginous conditions during the Ancylus Lake-to-Littorina Sea transition and HTM but with only brief excursions to intermittently or weakly euxinic conditions during this interval. At the western Baltic Proper sub-basin, Landsort Deep, new Fe and S isotope data bolster previous Mo isotope records and Fe speciation evidence for two distinct anoxic periods but also suggest that sulfide accumulation beyond transient levels was largely restricted to the sediment-water interface. Ultimately, the combined data from all three locations indicate that Fe enrichments typically indicative of euxinia may be best explained by Fe deposition as oxides following events likely analogous to the periodic incursions of oxygenated North Sea waters observed today, with subsequent pyrite formation in sulfidic pore waters. Additionally, the Mo isotope data from multiple Baltic Sea southern basins argue against restricted and widespread euxinic conditions, as has been demonstrated in the Baltic Proper and Bothnian Sea during the HTM or MCA. Instead, similar to today, each past Baltic anoxic event is characterized by redox conditions that become progressively more reducing with increasing distance from the sill.