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Topographic variation underpins a myriad of patterns and processes in hydrology, climatology, geography and ecology and is key to understanding the variation of life on the planet. A fully standardized and global multivariate product of different terrain features has the potential to support many large-scale basic research and analytical applications, however to date, such datasets are unavailable. Here we used the digital elevation model products of global 250 m GMTED2010 and near-global 90m SRTM4.1dev to derive a suite of topographic variables: elevation, slope, aspect, eastness, northness, roughness, terrain roughness index, topographic position index, vector ruggedness measure, profile/tangential curvature, first/second order partial derivative, and 10 geomorphological landform classes. We aggregated each variable to 1, 5, 10, 50 and 100 km spatial grains using several aggregation approaches. While a cross-correlation underlines the high similarity of many variables, a more detailed view in four mountain regions reveals local differences, as well as scale variations in the aggregated variables at different spatial grains.

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.

We report the levels of airborne individual PCB concentrations of gas and particle phases from the City of Chicago in 2009. Twenty-seven and 17 locations were sampled for gas and particle phases, respectively, where 141 and 46 gas and particle phases were collected. Total suspended particles (TSP) were also measured for the particle-phase samples. One hundred and seventy-one individual or coeluting congener PCBs are reported. Field blank masses for all 171 individual congeners for both gas (XAD-2) and particle (QFF) phases are included. Sample mass for all 171 individual congeners for both gas (XAD-2) and particle (QFF) phases are included. Deployment time and sampling flow are included. Final individual PCB congener concentrations, as well as ambient air temperature (K), wind speed (m/s), and TSP are included.

Methane (CH4) is a strong greenhouse gas known to have perturbed global climate in the past, especially when released in large quantities over short time periods from continental or marine sources. It is therefore crucial to understand and, if possible, quantify the individual and combined response of these variable methane sources to natural climate variability. However, past changes in the stability of greenhouse gas reservoirs remain uncertain and poorly constrained by geological evidence. Here, we present a record from the Congo fan of a highly specific bacteriohopanepolyol (BHP) biomarker for aerobic methane oxidation (AMO), 35-aminobacteriohopane-30,31,32,33,34-pentol (aminopentol), that identifies discrete periods of increased AMO as far back as 1.2 Ma. Fluctuations in the concentration of aminopentol, and other 35-aminoBHPs, follow a pattern that correlates with late Quaternary glacial-interglacial climate cycles, with highest concentrations during warm periods. We discuss possible sources of aminopentol, and the methane consumed by the precursor methanotrophs, within the context of the Congo River setting, including supply of methane oxidation markers from terrestrial watersheds and/or marine sources (gas hydrate and/or deep subsurface gas reservoir). Compound-specific carbon isotope values of -30 per mil to -40 per mil for BHPs in ODP 1075 and strong similarities between the BHP signature of the core and surface sediments from the Congo estuary and floodplain wetlands from the interior of the Congo River Basin, support a methanotrophic and likely terrigenous origin of the 35-aminoBHPs found in the fan sediments. This new evidence supports a causal connection between marine sediment BHP records of tropical deep sea fans and wetland settings in the feeding river catchments, and thus tropical continental hydrology. Further research is needed to better constrain the different sources and pathways of methane emission. However, this study identifies the large potential of aminoBHPs, in particular aminopentol, to trace and, once better calibrated and understood, quantify past methane sources and fluxes from terrestrial and potentially also marine sources.

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