The location and magnitude of oceanic iron sources remain uncertain owing to a scarcity of data, particularly in the Arctic Ocean. The formation of cold, dense water in the subsurface layer of the western Arctic Ocean is a key process in the lateral transport of iron, macronutrients, and other chemical constituents. Here, we present iron, humic-like fluorescent dissolved organic matter, and nutrient concentration data in waters above the continental slope and shelf and along two transects across the shelf–basin interface in the western Arctic Ocean. We detected high concentrations in shelf bottom waters and in a plume that extended in the subsurface cold dense water of the halocline layer in slope and basin regions. At σθ = 26.5, dissolved Fe, humic-like fluorescence intensity, and nutrient maxima coincided with N* minima (large negative values of N* indicate significant denitrification within shelf sediments). These results suggest that these constituents are supplied from the shelf sediments and then transported laterally to basin regions. Humic dissolved organic matter probably plays the most important role in the subsurface maxima and lateral transport of dissolved Fe in the halocline layer as natural Fe-binding organic ligand.

Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) is used in chemical oceanography to measure the organic complexation of metal ions in seawater. The bioactive trace metals iron, copper, cobalt, nickel, and zinc are all complexed (up to > 99% of iron and copper) by organic ligands in seawater (van den Berg and Nimmo 1987;Coale and Bruland 1988;Bruland 1989;Gledhill and van den Berg 1994;Rue and Bruland 1995;Wu and Luther 1995;Ellwood and van den Berg 2001), which can control solubility and bioavailability of these elements. Measuring the organic complexation of trace metals is, thus, an exceedingly important component of their biogeochemistry. To date, CLE-ACSV is the only widely accepted technique employed for measuring dissolved metalbinding ligand concentrations ([L i ]) in seawater and the conditional stability constants ( ) for their complexes with the metal of interest (M).To accomplish this, CLE-ACSV employs a well-characterized added ligand (AL) to compete against ambient ligands for M over a complete titration of a buffered seawater sample with additions of inorganic metal (M¢; typically from + 0 to + 10 ¥ [M]). Following equilibrium first with the metal additions (typically several hours) and then with the added ligand (minutes to hours), the resulting M(AL) x complex for each titration point is adsorbed to the surface of a hanging mercury drop electrode (HMDE) at a set voltage potential over a deposition time prede- AbstractCharacterization of the speciation of iron and copper is an important objective of the GEOTRACES Science Plan. To incorporate speciation measurements into such a multinational program, standard practices must be adopted that allow data from multiple labs to be synthesized. Competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) is the primary technique employed for measuring metal-binding ligands and determining metal speciation in seawater. The determination of concentrations and conditional stability constants of metal-binding ligands is particularly challenging, as results can be influenced both by experimental conditions and interpretation of titration data. Here, we report an investigation between four laboratories to study the speciation of iron and copper using CLE-ACSV. Samples were collected on the GEOTRACES II intercomparison cruise in the North Pacific Ocean in May 2009 at 30° N, 140° W. This intercomparison was carried out shipboard and included an assessment of the viability of sample preservation by freezing. Results showed that consensus values could be obtained between different labs, but that some existing practices were problematic and require further attention in future work. A series of recommendations emerged from this study that will be useful in implementing multi-investigator programs like GEOTRACES.

Distributions of trace metals (Mn, Fe, Ni, Zn and Cd) in the western Arctic Ocean (Chukchi Sea and Canada Basin) in September 2012 were investigated to elucidate the mechanisms behind the transport of these metals from the Chukchi Shelf to the Canada Basin. Filtered (< 0.22 μm) and unfiltered seawater samples were analyzed to determine dissolved (D) and total dissolvable (TD) trace metal concentrations, respectively. We identified maxima in vertical profiles for the concentrations of D-Fe and TD-Fe, as well as for the other four analyzed trace metals, which occurred in the halocline and/or near-bottom waters. Concentration profiles of all trace metals except for Cd also tended to show peaks near the surface, which suggest that the inflow of low-salinity Pacific-origin water from the Bering Strait, as well as local fresh water inputs such as river water and melting sea-ice, influenced trace metal concentrations. The distribution patterns and concentration ranges were generally similar between the D and TD fractions for Ni, Zn and Cd, which indicate that Ni, Zn and Cd were present mainly in their dissolved forms, whereas the concentrations of TD-Fe and TD-Mn were generally higher than those of D-Fe and D-Mn, respectively. These results are consistent with the results of previous studies of this region. For both Fe and Mn, labile particulate (LP) concentrations (the difference between the TD and D fractions, which is acid-leachable fraction in the particles during storage at pH 1.5-1.6) were highest in the nearbottom waters of the Chukchi Shelf region. The relationships between the distance from the shelf break and the concentrations of trace metals revealed that Fe and Mn concentrations in halocline waters tended to decrease logarithmically with distance, whereas changes in the concentrations of Ni, Zn, Cd and phosphate with distance were small. These results suggest that the distributions of Fe and Mn were controlled mainly by input from shelf sediment and removal through scavenging processes. Based on the phase distributions of Fe and Mn, which were calculated as ratios between the LP and D fractions, different behaviors between Fe and Mn were expressed during lateral transportation. The concentration of TD-Fe declined rapidly via removal of LP-Fe from the water column, whereas the concentration of TD-Mn declined more slowly through the transformation of D-Mn into LP-Mn. In contrast, the concentrations of D-Cd, D-Zn and D-Ni were more strongly correlated with phosphate levels, which suggest that, like phosphate, the distributions of Cd, Zn and Ni were generally controlled by the internal biogeochemical cycles of the ocean interior. Based on the findings of studies that have previously evaluated the concentration maxima of Ni, Zn and Cd within the halocline layer in the Canada Basin near the Canadian Arctic Archipelago, the elevated Ni, Zn and Cd concentrations in the halocline layer may extend across the Canada Basin from the Chukchi Sea shelf-break area. The determination coefficients for correlations with phosp...

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...