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PreprintCadmium isotope variations in the Southern Ocean( 2013-09-09) Xue, Zichen ; Rehkamper, Mark ; Horner, Tristan J. ; Abouchami, Wafa ; Middag, Rob ; van de Flierdt, Tina ; Baar, Hein J. W. deCadmium 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.
PreprintTowards an understanding of thallium isotope fractionation during adsorption to manganese oxides( 2013-04-22) Nielsen, Sune G. ; Wasylenki, Laura E. ; Rehkamper, Mark ; Peacock, Caroline L. ; Xue, Zichen ; Moon, Ellen M.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.