Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Benthic community structure and sediment processes on an intertidal flat: results from the ECOFLAT project

Interactions between physical and biological processes in intertidal sediments have been the focus of studies in the framework of the ECOFLAT project. Process studies were focused on the Molenplaat, a 1.5 km² intertidal flat in the Westerschelde estuary, The Netherlands. Distinct spatial patterns in the biological community on the flat were found and related to patterns in bottom shear stress as derived from a hydrodynamic model. Based on these survey results five stations were selected with contrasting sediment composition and benthic communities.Long-term net sedimentation of mainly sand was deduced from radionuclide profiles. Sedimentation of mud on the surface of part of the intertidal flat was shown to be a seasonally cyclic process, with a magnitude sufficient to significantly affect the mud balance of the estuary. Measurements of erodability as a function of tidal current showed a biological control on this variable. Benthic microalgae stabilise the sediment surface, whereas the benthic macrofauna has a destabilising effect.Food web studies show that the contrasting biological communities (microbenthos, meiobenthos, macrobenthos) at muddy and sandy sites have substantial differences in the quantitative aspects of their food web. Turnover of microalgae is much lower at muddy than at sandy sites, and this is mostly related to a lower grazing pressure. It is hypothesised that high mud content decreases the availability of benthic microalgae to grazers.We demonstrate a positive feedback between benthic microalgae and mud sedimentation which may lead to the existence of different stable states. This may explain the existence of relatively sharp boundaries and strong community contrasts in the presence of weak and smooth environmental gradients.     

The influence of porosity gradients on mixing coefficients in sediments

The surface layer of aquatic sediments is a zone characterized by both porosity gradients and intensive mixing. In the standard approach, porosity gradients are ignored when estimating mixing intensity. Here, model formulations with both constant and varying porosity are contrasted to estimate mixing coefficients D_b from tracer depth profiles. Complementing the well-known exponential solution of the constant-porosity model, we present a general solution to the variable-porosity model in terms of hypergeometric functions. When using these models in a forward way, the tracer activities predicted by the variable-porosity model are higher than those generated by the constant-porosity model. Similarly, when inverse modelling, D_b values estimated by the variable-porosity model are systematically higher than those derived from the constant-porosity model. Still, differences in D_b values remain relatively small. When applying both mixing models to excess ²¹⁰Pb data profiles from slope sediments, a maximal difference of 30% is obtained between D_b values, the average deviation being 16%. A systematic exploration of parameter space predicts a maximal underestimation of 60% when deriving D_b values from the constant-porosity mixing model. Given the uncertainty imposed by other model assumptions underlying the diffusive mixing model, the influence of porosity gradients on D_b values must be classified as rather modest. Hence, the current mixing coefficient database is not biased by the constant porosity approximation.     

Phosphorus Cycling and Burial in Sediments of a Seasonally Hypoxic Marine Basin

Recycling of phosphorus (P) from sediments contributes to the development of bottom-water hypoxia in many coastal systems. Here, we present results of a year-long assessment of P dynamics in sediments of a seasonally hypoxic coastal marine basin (Lake Grevelingen, the Netherlands) in 2012. Sequential phosphorus extractions (SEDEX) and X-ray absorption spectroscopy (XAS) indicate that P was adsorbed to Fe-(III)-(oxyhydr)oxides when cable bacteria were active in the surface sediments in spring. With the onset of summer hypoxia, sulphide-induced dissolution of the Fe-(III)-(oxyhydr)oxides led to P release to the pore water and overlying water. The similarity in authigenic Ca-P concentrations in the sediment and suspended matter suggest that Ca-P is not formed in situ. The P burial efficiency was ≤ 32%. Hypoxia-driven sedimentary P recycling had a major impact on the water-column chemistry in the basin in 2012. Water-column monitoring data indicate up to ninefold higher surface water concentrations of phosphate in the basin in the late 1970s and a stronger hypoxia-driven seasonal P release from the sediment. The amplified release of P from the sediment in the past is attributed to the presence of a larger pool of Fe-bound P in the basin prior to the first onset of hypoxia. Given that P is not limiting, primary production in the basin has not been affected by the decadal changes in P availability and recycling over the past 40 years. The changes in P dynamics on decadal time scales were not recorded in sediment profiles of total P or organic C/total P.     

Fossilization and degradation of intact polar lipids in deep subsurface sediments: A theoretical approach

Intact polar membrane lipids (IPLs) are frequently used as markers for living microbial cells in sedimentary environments. The assumption with these studies is that IPLs are rapidly degraded upon cell lysis and therefore IPLs present in sediments are derived from in situ microbial production. We used a theoretical approach to assess whether IPLs in surface sediments can potentially represent fossilized IPLs derived from the upper part of the water column and whether IPLs can be preserved during sediment burial. Previous studies which examined the degradation kinetics of IPLs show that phospholipids, i.e. ester-linked lipids with a phosphor-containing head group, degrade more rapidly than glycosidic ether lipids, i.e. ether-linked lipids with a glycosidically bound sugar moiety. Based on these studies, we calculate that only a minor fraction of phospholipids but a major fraction of glycosidic ether lipids biosynthesized in the upper part of the water column can potentially reach deep-sea surface sediments. Using a simple model and power law kinetic degradation parameters reported in the literature, we also evaluated the degradation of IPLs during sediment burial. Our model predicts a log-log relationship between IPL concentrations and depth, consistent with what has been observed in studies of IPLs in subsurface sediments. Although our results do not exclude production of IPLs in subsurface sediment, they do suggest that IPLs present in the deep biosphere may contain a substantial fossil component potentially masking in situ IPL production.