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...

The radiotracer 64 Cu was used to assess the influence of natural organic ligands on the bioavailability of copper. Biological availability of the 64 Cu-complexes was measured by accumulation in the bivalve Macoma balthica. The experiments were carried out in April as well as in February with water from the relatively clean Oosterschelde Sea arm and the relatively polluted Westerschelde estuary. Adsorption onto shells, as well as uptake in tissues was assessed at salinities of 10%o and 30%o. Simultaneously with the exposure experiments, ligand characteristics of the natural waters were assessed. High ligand concentrations, as occurring in the Westerschelde around February, reduced 64 Cu (320 nM) uptake by more than 50%, in spite of the much lower salinity in the Westerschelde water. At the low salinity, uptake was increased slightly in Westerschelde water, but considerably in Oosterschelde water. This implies that at low ambient ligand concentrations (during the whole year in Oosterschelde water and in the summer period also in Westerschelde water) the influence of salinity on 64 Cu uptake is more pronounced.

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