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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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Iron (oxyhydr)oxides (FeOx) control retention of dissolved nutrients and contaminants in aquatic systems. However, FeOx structure and reactivity is dependent on adsorption and incorporation of such dissolved species, particularly oxyanions such as phosphate and silicate. These interactions affect the fate of nutrients and metal(loids), especially in perturbed aquatic environments such as eutrophic coastal systems and environments impacted by acid mine drainage. Altered FeOx reactivity impacts sedimentary nutrient retention capacity and, eventually, ecosystem trophic state. Here, we explore the influence of phosphate (P) and silicate (Si) on FeOx structure and reactivity. Synthetic, poorly crystalline FeOx with adsorbed and coprecipitated phosphate or silicate at low but environmentally relevant P/Fe or Si/Fe ratios (0.02-0.1 mol mol-1) was prepared by base titration of Fe(III) solutions. Structural characteristics of FeOx were investigated by X-ray diffraction, synchrotron-based X-ray absorption spectroscopy and high-energy X-ray scattering. Reactivity of FeOx was assessed by kinetic dissolution experiments under acidic (dilute HCl, pH 2) and circumneutral reducing (bicarbonate-buffered ascorbic acid, pH 7.8, Eh ~-300 mV) conditions. At these loadings, phosphate and silicate coprecipitation had only slight impact on local and intermediate-ranged FeOx structure, but significantly enhanced the dissolution rate of FeOx. Conversely, phosphate and silicate adsorption at similar loadings resulted in particle surface passivation and decreased FeOx dissolution rates. These findings indicate that varying nutrient loadings and different interaction mechanisms between anions and FeOx (adsorption versus coprecipitation) can influence the broader biogeochemical functioning of aquatic ecosystems by impacting the structure and reactivity of FeOx.

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A high energy resolution x-ray absorption near-edge structure ͑XANES͒ spectroscopy study on U 4+ ͑UO 2 ͒, U 5+ ͓͑UO 2 Py 5 ͔͓KI 2 Py 2 ͔͒, and U 6+ ͓UO 2 ͑NO 3 ͒ 2 ͑H 2 O͒ 6 ͔ demonstrates the potential of this experimental technique for qualitative/semiqualitative and quantitative actinide speciation investigations. We observe a pre-edge feature with quadrupole nature in a U L 3 edge partial fluorescence yield-XANES spectrum. This feature is a tool for characterizing the participation of 5f orbitals in U-O bonding. The feature origin is explained by performing calculations with the finite difference method near-edge structure code based on the multiplescattering theory and the finite difference method.