The GEOTRACES Intermediate Data Product 2014 (IDP2014) is the first publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2013. It consists of two parts: (1) a compilation of digital data for more than 200 trace elements and isotopes (TEls) as well as classical hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing a strongly inter-linked on-line atlas including more than 300 section plots and 90 animated 3D scenes. The IDP2014 covers the Atlantic, Arctic, and Indian oceans, exhibiting highest data density in the Atlantic. The TEI data in the IDP2014 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at cross-over stations. The digital data are provided in several formats, including ASCII spreadsheet, Excel spreadsheet, netCDF, and Ocean Data View collection. In addition to the actual data values the IDP2014 also contains data quality flags and 1-sigma data error values where available. Quality flags and error values are useful for data filtering. Metadata about data originators, analytical methods and original publications related to the data are linked to the data in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2014 data providing section plots and a new kind of animated 3D scenes. The basin-wide 3D scenes allow for viewing of data from many cruises at the same time, thereby providing quick overviews of large-scale tracer distributions. In addition, the 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of observed tracer plumes, as well as for making inferences about controlling processes. (C) 2015 The Authors. Published by Elsevier B.V
We report isotope dilution analyses of dissolved cadmium (Cd) and electrochemical Cd speciation measurements in the Atlantic sector of the Southern Ocean. Bioavailable inorganic Cd is . 100 times higher in nearsurface waters south of the Polar Front compared to the Subantarctic Zone because of upwelling and reduced complexation by organic Cd ligands. To trace local changes in the relation between Cd and P, we examine the deviations from a linear deep-water Cd vs. P relation (Cd*), and find that changes in Cd* coincide with the position of frontal systems and covary with primary productivity and total dissolved Mn and Fe concentrations. These covariations agree with potential local changes in phytoplankton Cd uptake rates, resulting from differences in the availability of Cd, Zn, Mn, and Fe. A band of negative Cd* values is associated with formation of Subantarctic Mode Water (SAMW) and Antarctic Intermediate Water (AAIW). In contrast to SAMW, which may export low Cd : P ratios from the Southern Ocean, the Cd : P ratios in AAIW increase by mixing with underlying Upper Circumpolar Deep Water before being exported from the Southern Ocean. Deep waters show constant Cd : P ratios, and both elements behave conservatively with end-member mixing between deep waters of the Weddell Gyre, the Antarctic Circumpolar Current, and inflowing North Atlantic Deep Water. Overall, our results support the hypothesis that the kink in the global Cd vs. P relation is largely caused by high Cd : P uptake ratios in the trace-nutrient-limited Southern Ocean.
a b s t r a c tWith the common goal of more accurately and consistently quantifying ambient concentrations of free metal ions and natural organic ligands in aquatic ecosystems, researchers from 15 laboratories that routinely analyze trace metal speciation participated in an intercomparison of statistical methods used to model their most common type of experimental dataset, the complexometric titration. All were asked to apply statistical techniques that they were familiar with to model synthetic titration data that are typical of those obtained by applying stateof-the-art electrochemical methods -anodic stripping voltammetry (ASV) and competitive ligand equilibration-adsorptive cathodic stripping voltammetry (CLE-ACSV) -to the analysis of natural waters. Herein, we compare their estimates for parameters describing the natural ligands, examine the accuracy of inferred ambient free metal ion concentrations ([M f ]), and evaluate the influence of the various methods and assumptions used on these results. The ASV-type titrations were designed to test each participant's ability to correctly describe the natural ligands present in a sample when provided with data free of measurement error, i.e., random noise. For the three virtual samples containing just one natural ligand, all participants were able to correctly identify the number of ligand classes present and accurately estimate their parameters. For the four samples containing two or three ligand classes, a few participants detected too few or too many classes and consequently reported inaccurate 'measurements' of ambient [M f ]. Since the problematic results arose from human error rather than any specific method of analyzing the data, we recommend that analysts should make a practice of using one's parameter estimates to generate simulated (back-calculated) titration curves for comparison to the original data. The root-meansquared relative error between the fitted observations and the simulated curves should be comparable to the expected precision of the analytical method and upon visual inspection the distribution of residuals should not be skewed.Marine Chemistry 173 (2015) 3-24 BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Modeling the synthetic, CLE-ACSV-type titration dataset, which comprises 5 titration curves generated at different analytical windows or levels of competing ligand added to the virtual sample, proved to be more challenging due to the random measurement error that was incorporated. Comparison of the submitted results was complicated by the participants' differing interpretations of their task. Most adopted the provided 'true' instrumental sensitivity in modeling the CLE-ACSV curves, but several estimated sensitivities using internal calibration, exactly as is required for actual samples. Since most fitted sensitivities were biased low, systematic error in inferred ambient [M f ] and in estimated weak ligand (L 2 ) concentrations resulted. The main distinction between the mathematical approaches taken by participants lie...
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