Description: Author Posting. © The Author(s), 2008. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Marine Chemistry 112 (2008): 149-157, doi:10.1016/j.marchem.2008.09.004.

Description: Cadmium is a biologically important trace metal that co-varies with phosphate (PO43- or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remains elusive. Here, we present a time series study of Cd and PO43- from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO43- in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO43- water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (αCd-P) determined by the local environment can be used to account for the Cd/PO43- relationship in different parts of the ocean. The high Cd/PO43- of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO43- ratio of the Southern Ocean will vary on glacial-interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO43- in seawater arise from changes in population structure and community requirements for macro- and micronutrients.

Description: The work was funded as part of NERC Antarctic Funding Initiative AFI4-02. KRH is funded by NERC grant NER/S/A/2004/12390.

Description: Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V for personal use, not for redistribution. The definitive version was published in Earth and Planetary Science Letters 382 (2013): 161-172, doi:10.1016/j.epsl.2013.09.014.

Description: Cadmium concentrations and isotope compositions were determined for 47 seawater samples from the high nutrient low chlorophyll (HNLC) zone of the Atlantic sector of the Southern Ocean. The samples include 13 surface waters from a transect of the Weddell Gyre and 3 depth profiles from the Weddell Sea and Drake Passage. The Southern Ocean mixed layer samples from this study and Abouchami et al. (2011) define a clear but broad ‘HNLC trend’ in a plot of ε114/110Cd versus [Cd], which is primarily a consequence of isotopic fractionation associated with biological uptake (ε114/110Cd is the deviation of the 114Cd/110Cd ratio of a sample from NIST SRM 3108 Cd in parts per 10,000). The trend is especially apparent in comparison to the large range of values shown by a global set of seawater Cd data for shallow depths. The Southern Ocean samples are also distinguished by their relatively high Cd concentrations (typically 0.2 to 0.6 nmol/kg) and moderately fractionated ε114/110Cd (generally between +4 and +8) that reflect the limited biological productivity of this region. Detailed assessment reveals fine structure within the ‘HNLC trend’, which may record differences in the biological fractionation factor, different scenarios of closed and open system isotope fractionation, and/or distinct source water compositions. Southern Ocean seawater from depths ≥1000 m has an average ε114/110Cd of +2.5 ± 0.2 (2se, n = 16), and together with previous results this establishes a relatively constant ε114/110Cd value of +3.0 ± 0.3 (2se, n = 27) for global deep waters. Significant isotopic variability was observed at intermediate depths in the Southern Ocean. Seawater from 200 m to 400 m in Weddell Sea has high Cd concentrations and ε114/110Cd as low as +1, presumably due to remineralization of Cd from biomass that records incomplete nutrient utilization. Antarctic Intermediate Water, which was sampled at 150 to 750 m depth in the Drake Passage, features a distinct Cd isotope signature of ε114/110Cd ≈ +4, which reflects biological isotope fractionation at the surface and subsequent mixing into the ocean interior. Taken together, our results demonstrate that coupled Cd isotope and concentration data provide valuable insights into the distribution and biological cycling of Cd in the water column. The highly systematic nature 55 of Cd isotope signatures may furthermore prove to be of utility for future research in marine geochemistry and paleoceanography.

Description: This research was supported by NERC grant NE/G008973/1.

Description: Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 117 (2013): 252–265, doi:10.1016/j.gca.2013.05.004.

Description: We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments is smaller than observed between seawater and natural sediments. The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297-313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated sites, and those proportions are controlled by how much total Tl is sorbed per unit of birnessite. In the experiments with the lowest initial Tl concentrations in solution (~0.15-0.4 μg/g) and the lowest concentrations of Tl in the resulting Tl-sorbed birnessite (≤17 μg Tl/mg birnessite), we observed the largest isotopic fractionations, and fractionation is inversely proportional to the initial aqueous Tl concentration. Again, this correlation can be explained by the simultaneous occupation of two different sorption sites; vacancy sites that carry isotopically fractionated Tl and a second site carrying slightly fractionated Tl. The fractionation factors observed in nature exceed those in the experiments likely because the Tl concentrations in seawater and in ferromanganese sediments are three to four orders of magnitude lower than in our experiments, and therefore the second slightly fractionated sorption site is not significantly utilized. Temperature (6°C to 40°C) and experimental duration (3 min to 72 hr) appear to have little or no effects on isotope behaviour in this system.

Description: This study was supported in part by NSF-OCE grant 0526618 to LW and a NERC fellowship to SGN. CLP acknowledges NERC grant NE/F00043X/1 and Royal Society grant RG072164. EMM was supported by a NERC studentship.

Description: © The Author(s), 2015. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Marine Chemistry 177 (2015): 1-8, doi:10.1016/j.marchem.2015.04.005.

Description: 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 (TEIs) 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-σ 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.

Description: We gratefully acknowledge financial support by the Scientific Committee on Oceanic Research (SCOR) through grants from the U.S. National Science Foundation, including grants OCE-0608600, OCE-0938349, and OCE-1243377. Financial support was also provided by the UK Natural Environment Research Council, the Ministry of Earth Science of India, the Centre National de Recherche Scientifique, l'Université Paul Sabatier de Toulouse, the Observatoire Midi-Pyrénées Toulouse, the Universitat Autònoma de Barcelona, the Kiel Excellence Cluster The Future Ocean, the Swedish Museum of Natural History, The University of Tokyo, The University of British Columbia, The Royal Netherlands Institute for Sea Research, the GEOMAR-Helmholtz Centre for Ocean Research Kiel, and the Alfred Wegener Institute.

Description: Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 653-665, doi:10.4319/lom.2012.10.653.

Description: We report data on the isotopic composition of cadmium, copper, iron, lead, zinc, and molybdenum at the GEOTRACES IC1 BATS Atlantic intercalibration station. In general, the between lab and within-lab precisions are adequate to resolve global gradients and vertical gradients at this station for Cd, Fe, Pb, and Zn. Cd and Zn isotopes show clear variations in the upper water column and more subtle variations in the deep water; these variations are attributable, in part, to progressive mass fractionation of isotopes by Rayleigh distillation from biogenic uptake and/or adsorption. Fe isotope variability is attributed to heavier crustal dust and hydrothermal sources and light Fe from reducing sediments. Pb isotope variability results from temporal changes in anthropogenic source isotopic compositions and the relative contributions of U.S. and European Pb sources. Cu and Mo isotope variability is more subtle and close to analytical precision. Although the present situation is adequate for proceeding with GEOTRACES, it should be possible to improve the within-lab and between-lab precisions for some of these properties.

Description: The National Science Foundation sponsored the cruise and many of the shipboard participants; in particular E.B. was funded to participate on the cruise by NSF Grant OCE-0751409 and his preparation of this paper was partially supported by grants from the Kuwait Foundation for the Advancement of Science (KFAS) and the Singapore-MIT Alliance for Research and Technology (SMART).