• European Marine Science
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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.

A tool for multidimensional variational analysis (divand) is presented. It allows the interpolation and analysis of observations on curvilinear orthogonal grids in an arbitrary high dimensional space by minimizing a cost function. This cost function penalizes the deviation from the observations, the deviation from a first guess and abruptly varying fields based on a given correlation length (potentially varying in space and time). Additional constraints can be added to this cost function such as an advection constraint which forces the analysed field to align with the ocean current. The method decouples naturally disconnected areas based on topography and topology. This is useful in oceanography where disconnected water masses often have different physical properties. Individual elements of the a priori and a posteriori error covariance matrix can also be computed, in particular expected error variances of the analysis. A multidimensional approach (as opposed to stacking 2-dimensional analysis) has the benefit of providing a smooth analysis in all dimensions, although the computational cost is increased. Primal (problem solved in the grid space) and dual formulations (problem solved in the observational space) are implemented using either direct solvers (based on Cholesky factorization) or iterative solvers (conjugate gradient method). In most applications the primal formulation with the direct solver is the fastest, especially if an a posteriori error estimate is needed. However, for correlated observation errors the dual formulation with an iterative solver is more efficient. The method is tested by using pseudo observations from a global model. The distribution of the observations is based on the position of the ARGO floats. The benefit of the 3-dimensional analysis (longitude, latitude and time) compared to 2-dimensional analysis (longitude and latitude) and the role of the advection constraint are highlighted. The tool divand is free software, and is distributed under the terms of the GPL license (http://modb.oce.ulg.ac.be/mediawiki/index.php/divand). PREDANTAR, EMODNET Chemistry 2, SeaDataNet II

The dataset compiles pigment content, absorptance data, photosynthetic parameters and primary production data as proxies for summertime photoacclimation of the temperate intertidal eelgrass Zostera marina after a 25-day exposure to a natural light intensity gradient (6, 36, 74, 133, 355, 503 and 860 µmol photons/m²/s) under laboratory conditions at the Pointe-au-Père research station, East Rimouski, Quebec, Canada. The data bundle contains: 1) photosynthetic and total absorptance data at the end of the experiment, which respectively represent the fraction of incident visible light absorbed by the photosynthetic tissues corrected and not corrected for non-photosynthetic absorption; 2) pigment content at the end of the experiment, which includes chlorophyll a and b and total carotenoids contents; 3) photosynthetic parameters obtained by Rapid Light Curves (RLC) on days 5 and 25, including photosynthetic apparatus efficiency (alpha), capacity (ETRmax) and saturation (Ek); 4) whole shoot primary production at the end of the experiment, which was calculated from oxygen fluxes under light and dark conditions, and normalized by leaf surface.