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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 development of phosphate sensors suitable for long-term in situ deployments in natural waters, is essential to improve our understanding of the distribution, fluxes, and biogeochemical role of this key nutrient in a changing ocean. Here, we describe the optimization of the molybdenum blue method for in situ work using a lab-on-chip (LOC) analyzer and evaluate its performance in the laboratory and at two contrasting field sites. The in situ performance of the LOC sensor is evaluated using hourly time-series data from a 56-day trial in Southampton Water (UK), as well as a month-long deployment in the subtropical oligotrophic waters of Kaneohe Bay (Hawaii, USA). In Kaneohe Bay, where phosphate concentrations were characteristic of the dry season (0.13 ± 0.03 μM, n = 704), the in situ sensor accuracy was 16 ± 12% and a potential diurnal cycle in phosphate concentrations was observed. In Southampton Water, the sensor data (1.02 ± 0.40 μM, n = 1,267) were accurate to ±0.10 μM relative to discrete reference samples. Hourly in situ monitoring revealed striking tidal and storm derived fluctuations in phosphate concentrations in Southampton Water that would not have been captured via discrete sampling. We show the impact of storms on phosphate concentrations in Southampton Water is modulated by the spring-neap tidal cycle and that the 10-fold decline in phosphate concentrations observed during the later stages of the deployment was consistent with the timing of a spring phytoplankton bloom in the English Channel. Under controlled laboratory conditions in a 250 L tank, the sensor demonstrated an accuracy and precision better than 10% irrespective of the salinity (0–30), turbidity (0–100 NTU), colored dissolved organic matter (CDOM) concentration (0–10mg/L), and temperature (5–20◦C) of the water (0.3–13 μM phosphate) being analyzed. This work demonstrates that the LOC technology is mature enough to quantify the influence of stochastic events on nutrient budgets and to elucidate the role of phosphate in regulating phytoplankton productivity and community composition in estuarine and coastal regimes. Refereed 14.A Nutrients TRL 8 Actual system completed and "mission qualified" through test and demonstration in an operational environment (ground or space) Manual (incl. handbook, guide, cookbook etc) Standard Operating Procedure

Cable bacteria are multicellular, filamentous microorganisms that are capable of transporting electrons over centimeter-scale distances. Although recently discovered, these bacteria appear to be widely present in the seafloor, and when active they exert a strong imprint on the local geochemistry. In particular, their electrogenic metabolism induces unusually strong pH excursions in aquatic sediments, which induces considerable mineral dissolution, and subsequent mineral reprecipitation. However, at present, it is unknown whether and how cable bacteria play an active or direct role in the mineral reprecipitation process. To this end we present an explorative study of the formation of sedimentary minerals in and near filamentous cable bacteria using a combined approach of electron microscopy and spectroscopic techniques. Our observations reveal the formation of polyphosphate granules within the cells and two different types of biomineral formation directly associated with multicellular filaments of these cable bacteria: (i) the attachment and incorporation of clay particles in a coating surrounding the bacteria and (ii) encrustation of the cell envelope by iron minerals. These findings suggest a complex interaction between cable bacteria and the surrounding sediment matrix, and a substantial imprint of the electrogenic metabolism on mineral diagenesis and sedimentary biogeochemical cycling. In particular, the encrustation process leaves many open questions for further research. For example, we hypothesize that the complete encrustation of filaments might create a diffusion barrier and negatively impact the metabolism of the cable bacteria.

Changes in marine net primary productivity (PP) and export of particulate organic carbon (EP) are projected over the 21st century with four global coupled carbon cycle-climate models. These include representations of marine ecosystems and the carbon cycle of different structure and complexity. All four models show a decrease in global mean PP and EP between 2 and 20% by 2100 relative to preindustrial conditions, for the SRES A2 emission scenario. Two different regimes for productivity changes are consistently identified in all models. The first chain of mechanisms is dominant in the low- and mid-latitude ocean and in the North Atlantic: reduced input of macro-nutrients into the euphotic zone related to enhanced stratification, reduced mixed layer depth, and slowed circulation causes a decrease in macro-nutrient concentrations and in PP and EP. The second regime is projected for parts of the Southern Ocean: an alleviation of light and/or temperature limitation leads to an increase in PP and EP as productivity is fueled by a sustained nutrient input. A region of disagreement among the models is the Arctic, where three models project an increase in PP while one model projects a decrease. Projected changes in seasonal and interannual variability are modest in most regions. Regional model skill metrics are proposed to generate multi-model mean fields that show an improved skill in representing observation-based estimates compared to a simple multi-model average. Model results are compared to recent productivity projections with three different algorithms, usually applied to infer net primary production from satellite observations.

The age of organic material discharged by rivers provides information about its sources and carbon cycling processes within watersheds. While elevated ages in fluvially-transported organic matter are usually explained by erosion of soils and sediments, it is commonly assumed that mainly young organic material is discharged from flat tropical watersheds due to their extensive plant cover and high carbon turnover. Here we present compound-specific radiocarbon data of terrigenous organic fractions from a sedimentary archive offshore the Congo River in conjunction with molecular markers for methane-producing land cover reflecting wetland extent in the watershed. We find that the Congo River has been discharging aged organic matter for several thousand years with increasing ages from the mid- to the Late Holocene. This suggests that aged organic matter in modern samples is concealed by radiocarbon from nuclear weapons testing. By comparison to indicators for past rainfall changes we detect a systematic control of organic matter sequestration and release by continental hydrology mediating temporary carbon storage in wetlands. As aridification also leads to exposure and rapid remineralization of large amounts of previously stored labile organic matter we infer that this process may cause a profound direct climate feedback currently underestimated in carbon cycle assessments.

Sediments (spanning a minimum of 13.3 ka) from the St. Anna Trough (Northern Kara Sea). The site has experienced extensive fluctuation in the delivery of river-derived organic matter (OM), caused by a eustatic change in sea level. This is in line with the record of the concentration of the isoprenoid GDGT, crenarchaeol, produced by marine Thaumarchaota, which was low at the bottom of the core, increasing gradually in the most shallow unit. The concentration of branched (br)GDGTs showed an opposite trend and a marked shift in distribution. The deepest sediments (>10 ka), with a distribution currently encountered in surface sediments in front of the Yenisei River, are characterized by terrigenous brGDGTs, whereas the distribution in the shallowest unit (<10 ka) is strongly influenced by marine, in-situ brGDGTs. During the shift from terrigenous to marine-sourced brGDGTs, there was one horizon where a pronounced shift in the brGDGT distribution was observed and the brGDGT concentration significantly decreased. As the brGDGTs delivered to the current Kara Sea system are derived from several sources, we postulate that a temporary change in the relative importance of the brGDGT sources happened during this interval. Both in-situ production and changing brGDGT provenance have implications for paleoclimate reconstruction using brGDGTs. In-situ production of marine brGDGTs results in a higher reconstructed pH. However, these in-situ produced brGDGTs did not influence the reconstructed mean annual air temperature (MAT), when the MATmrs calibration was used. Changes in the relative contribution of brGDGT sub-pools were shown, however, to influence both soil pH reconstruction and MAT reconstruction.

In permafrost areas, seasonal freeze-thaw cycles result in upward and downward movements of the ground. For some permafrost areas, long-term downward movements were reported during the last decade. We measured seasonal and multi-year ground movements in a yedoma region of the Lena River Delta, Siberia, in 2013–2017, using reference rods installed deep in the permafrost. The seasonal subsidence was 1.7 ± 1.5 cm in the cold summer of 2013 and 4.8 ± 2 cm in the warm summer of 2014. Furthermore, we measured a pronounced multi-year net subsidence of 9.3 ± 5.7 cm from spring 2013 to the end of summer 2017. Importantly, we observed a high spatial variability of subsidence of up to 6 cm across a sub-meter horizontal scale. In summer 2013, we accompanied our field measurements with Differential Synthetic Aperture Radar Interferometry (DInSAR) on repeat-pass TerraSAR-X (TSX) data from the summer of 2013 to detect summer thaw subsidence over the same study area. Interferometry was strongly affected by a fast phase coherence loss, atmospheric artifacts, and possibly the choice of reference point. A cumulative ground movement map, built from a continuous interferogram stack, did not reveal a subsidence on the upland but showed a distinct subsidence of up to 2 cm in most of the thermokarst basins. There, the spatial pattern of DInSAR-measured subsidence corresponded well with relative surface wetness identified with the near infra-red band of a high-resolution optical image. Our study suggests that (i) although X-band SAR has serious limitations for ground movement monitoring in permafrost landscapes, it can provide valuable information for specific environments like thermokarst basins, and (ii) due to the high sub-pixel spatial variability of ground movements, a validation scheme needs to be developed and implemented for future DInSAR studies in permafrost environments.

Jellyfishes have functionally replaced several overexploited commercial stocks of planktivorous fishes. This is paradoxical, because they use a primitive prey capture mechanism requiring direct contact with the prey, whereas fishes use more efficient visual detection. We have compiled published data to show that, in spite of their primitive life-style, jellyfishes exhibit similar instantaneous prey clearance and respiration rates as their fish competitors and similar potential for growth and reproduction. To achieve this production, they have evolved large, water-laden bodies that increase prey contact rates. Although larger bodies are less efficient for swimming, optimization analysis reveals that large collectors are advantageous if they move through the water sufficiently slowly.

In the southern Indian Ocean, the position of the subtropical front – the boundary between colder, fresher waters to the south and warmer, saltier waters to the north – has a strong influence on the upper ocean hydrodynamics and biogeochemistry. Here we analyse a sedimentary record from the Agulhas Plateau, located close to the modern position of the subtropical front and use alkenones and coccolith assemblages to reconstruct oceanographic conditions over the past 300,000 years. We identify a strong glacial-interglacial variability in sea surface temperature and productivity associated with subtropical front migration over the Agulhas Plateau, as well as shorter-term high frequency variability aligned with variations in high latitude insolation. Alkenone and coccolith abundances, in combination with diatom and organic carbon records indicate high glacial export productivity. We conclude that the biological pump was more efficient and strengthened during glacial periods, which could partly account for the reported reduction in atmospheric carbon dioxide concentrations.