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Fe isotope ratios and concentrations of dissolved Fe (Fedis, < 0.45 μm) and of suspended particulate Fe (FeSPM) were analyzed from a depth profile through the anoxic Eastern Gotland Basin water column, Baltic Sea. Results show a sharp gradient in δ56Fedis across the ferruginous layer with δ56Fedis = −0.4‰ in the euxinic deep basin and δ56Fedis = +0.3‰ in the oxic upper water column. The isotopic gradient overlaps with a strong concentration gradient of Fedis, a concentration maximum in FeSPM and lower δ56FeSPM values than δ56Fedis. These features indicate preferential loss of light Fe isotopes from solution to suspended iron-oxyhydroxides (FeIOH) during typical oxidative precipitation across the redox interface. The sign of the overall fractionation, Δ56FeIOH-Fe(II)(aq) < 0‰, is in contrast to similar, mostly non-marine redox environments, where Δ56FeIOH-Fe(II)(aq) > 0‰. The difference appears to be the result of isotope exchange dominated by reaction kinetics in the marine water column, rather than equilibrium fractionation generally inferred for oxidative Fe precipitation elsewhere. High residual δ56Fedis immediately above the oxic–ferruginous interface and throughout the oxic water column suggests that any potential dissolved Fe export from marine reducing waters into the oxic open water column is enriched in the heavy isotopes. In the deep, mildly euxinic water column above the level of Fe sulfide saturation, a decreasing δ56FeSPM trend with depth and a generally low δ56Fedis are comparable to trends generally observed in marine anoxic sediment profiles where microbial reductive Fe dissolution occurs. The isotope composition of the redox-cycled Fe inventory in anoxic marine basins mainly reflects the balance between external fluxes, driving the composition towards crustal δ56Fe values, and intensity of internal recycling, driving δ56Fe towards negative values.

At the end of 2014, a major Baltic inflow (MBI) brought oxygenated, salty water into the Baltic proper and reached the long-term anoxic Eastern Gotland Basin (EGB) by March 2015. In July 2015, we measured benthic fluxes of phosphorus (P), nitrogen (N) and silicon (Si) nutrients and dissolved inorganic carbon (DIC) in situ using an autonomous benthic lander at deep sites (170-210 m) in the EGB, where the bottom water oxygen concentration was 30-45 µM. The same in situ methodology was used to measure benthic fluxes at the same sites in 2008-2010, but then under anoxic conditions. The high efflux of phosphate under anoxic conditions became lower upon oxygenation, and turned into an influx in about 50 % of the flux measurements. The C:P and N:P ratios of the benthic solute flux changed from clearly below the Redfield ratio (on average about 70 and 3-4, respectively) under anoxia to approaching or being well above the Redfield ratio upon oxygenation. These observations demonstrate retention of P in newly oxygenated sediments. We found no significant effect of oxygenation on the benthic ammonium, silicate and DIC flux. We also measured benthic denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) rates at the same sites using isotope-pairing techniques. The bottom water of the long-term anoxic EGB contained less than 0.5 µM nitrate in 2008-2010, but the oxygenation event created bottom water nitrate concentrations of about 10 µM in July 2015 and the benthic flux of nitrate was consistently directed into the sediment. Nitrate reduction to both dinitrogen gas (denitrification) and ammonium (DNRA) was initiated in the newly oxygenated sediments, while anammox activity was negligible. We estimated the influence of this oxygenation event on the magnitudes of the integrated benthic P flux (the internal P load) and the fixed N removal through benthic and pelagic denitrification by comparing with a hypothetical scenario without the MBI. Our calculations suggest that the oxygenation triggered by the MBI in July 2015, extrapolated to the basin-wide scale of the Baltic proper, decreased the internal P load by 23% and increased the total (benthic plus pelagic) denitrification by 18%.