a b s t r a c t Phosphorus (P) is an essential nutrient for marine organisms. Its burial in hypoxic and anoxic marine basins is still incompletely understood. Recent studies suggest that P can be sequestered in sediments of such basins as reduced iron (Fe)-P but the exact phase and the underlying mechanisms that lead to its formation are unknown. In this study, we investigated sediments from the deepest basin in the Baltic Sea, the Landsort Deep (site M0063), that were retrieved during the Integrated Ocean Drilling Project (IODP) Baltic Sea Paleoenvironment Expedition 347. The record comprises the whole brackish/marine Littorina Sea stage including past intervals of extensive hypoxia in the Baltic Sea that occurred during the Holocene Thermal Maximum (HTM HI ) and the Medieval Climate Anomaly (MCA1 HI and MCA2 HI ). Various redox proxies (e.g. the presence of laminations and high Mo contents) suggest almost permanent bottom water hypoxia during the Littorina Sea stage in the Landsort Deep. The bottom waters were likely even seasonally anoxic or sulfidic during the MCA1 HI and MCA2 HI , and permanently sulfidic during the HTM HI . With the use of micro-analysis of sieved minerals (SEM-EDS, XRD and synchrotron-based XAS), we show that Mn-and Mgrich vivianite crystals are present at various depths in the Littorina Sea sediments. We also have indications for vivianite in the MCA1 HI , MCA2 HI and HTM HI deposits. The formation of vivianite thus likely explains the high Febound P fraction throughout the whole Littorina Sea stage. Shuttling of Fe and Mn from the shelves into the basin and high inputs of P in settling organic matter are likely key drivers for vivianite formation. Our study shows that vivianite can likely form in near-surface sediments under a broad range of bottom water redox conditions, varying from hypoxic and anoxic to sulfidic.

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Phosphorus (P) is a key nutrient for marine organisms. The only long-term removal pathway for P in the marine realm is burial in sediments. Iron (Fe) bound P accounts for a significant proportion of this burial at the global scale. In sediments underlying anoxic bottom waters, burial of Fe-bound P is generally assumed to be negligible because of reductive dissolution of Fe(III) (oxyhydr)oxides and release of the associated P. However, recent work suggests that Fe-bound P is an important burial phase in euxinic (i.e. anoxic and sulfidic) basin sediments in the Baltic Sea. In this study, we investigate the role of Fe-bound P as a potential sink for P in Black Sea sediments overlain by oxic and euxinic bottom waters. Sequential P extractions performed on sediments from six multicores along two shelf-to-basin transects provide evidence for the burial of Fe-bound P at all sites, including those in the euxinic deep basin. In the latter sediments, Fe-bound P accounts for more than 20% of the total sedimentary P pool. We suggest that this P is present in the form of reduced Fe-P minerals. We hypothesize that these minerals may be formed as inclusions in sulfur-disproportionating Deltaproteobacteria. Further research is required to elucidate the exact mineral form and formation mechanism of this P burial phase, as well as its role as a sink for P in sulfide-rich marine sediments.

Salinity variations in restricted basins like the Baltic Sea can alter their vulnerability to hypoxia (i.e., bottom water oxygen concentrations <2 mg/l) and can affect the burial of phosphorus (P), a key nutrient for marine organisms. We combine porewater and solid-phase geochemistry, microanalysis of sieved sediments (including XRD and synchrotron-based XAS), and foraminiferal δ 18 O and δ 13 C analyses to reconstruct the bottom water salinity, redox conditions, and P burial in the Ångermanälven estuary, Bothnian Sea. Our sediment records were retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013. We demonstrate that bottom waters in the Ångermanälven estuary became anoxic upon the intrusion of seawater in the early Holocene, like in the central Bothnian Sea. The subsequent refreshening and reoxygenation, which was caused by gradual isostatic uplift, promoted P burial in the sediment in the form of Mn-rich vivianite. Vivianite authigenesis in the surface sediments of the more isolated part of the estuary ultimately ceased, likely due to continued refreshening and an associated decline in productivity and P supply to the sediment. The observed shifts in environmental conditions also created conditions for postdepositional formation of authigenic vivianite, and possibly apatite formation, at ∼8 m composite depth. These salinityrelated changes in redox conditions and P burial are highly relevant in light of current climate change. The results specifically highlight that increased freshwater input linked to global warming may enhance coastal P retention, thereby contributing to oligotrophication in both coastal and adjacent open waters.

Abstract. Phosphorus (P) concentrations in sediments are frequently used to reconstruct past environmental conditions in freshwater and marine systems, with high values thought to be indicative of a high biological productivity. Recent studies suggest that the post-depositional formation of vivianite, an iron(II)-phosphate mineral, might significantly alter trends in P with sediment depth. To assess its importance, we investigate a sediment record from the Bornholm Basin that was retrieved during the Integrated Ocean Drilling Program (IODP) Baltic Sea Paleoenvironment Expedition 347 in 2013, consisting of lake sediments overlain by brackish-marine deposits. Combining bulk sediment geochemistry with microanalysis using scanning electron microscope energy dispersive spectroscopy (SEM-EDS) and synchrotron-based X-ray absorption spectroscopy (XAS), we demonstrate that vivianite-type minerals rich in manganese and magnesium are present in the lake deposits just below the transition to the brackish-marine sediments (at 11.5 to 12 m sediment depth). In this depth interval, phosphate that diffuses down from the organic-rich, brackish-marine sediments meets porewaters rich in dissolved iron in the lake sediments, resulting in the precipitation of iron(II) phosphate. Results from a reactive transport model suggest that the peak in iron(II) phosphate originally occurred at the lake-marine transition (9 to 10 m) and moved downwards due to changes in the depth of a sulfidization front. However, its current position relative to the lake-marine transition is stable as the vivianite-type minerals and active sulfidization fronts have been spatially separated over time. Experiments in which vivianite was subjected to sulfidic conditions demonstrate that incorporation of manganese or magnesium in vivianite does not affect its susceptibility to sulfide-induced dissolution. Our work highlights that post-depositional formation of iron(II) phosphates such as vivianite has the potential to strongly alter sedimentary P records particularly in systems that are subject to environmental perturbation, such as a change in primary productivity, which can be associated with a lake-marine transition.

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