Iron and manganese shuttle has no effect on sedimentary thallium and vanadium isotope signatures in Black Sea sediments

Abstract

Thallium and V isotopes in organic-rich sediments have recently been explored for reconstructing marine oxygenation by tracking the burial of Mn oxides either locally or globally. The ‘Fe and Mn shuttle’ is a well known mechanism that can transport elements associated with Fe and Mn oxide phases formed under mildly oxidizing shallow water environments both laterally and vertically to euxinic (sulfidic water column) deep waters. The Fe and Mn shuttle has been demonstrated to strongly affect Fe and Mo isotope compositions of sediments accumulating beneath anoxic and euxinic settings. Similar to Mo, Tl and V are also enriched in oceanic ferromanganese crust and nodules, which impart the largest isotopic offsets from modern seawater for Tl and V. Thus, the mechanism of an Fe and Mn shuttle has the potential to, but currently unconstrained, affect Tl and V isotopic compositions (ε205Tl and δ51V) in organic-rich sediments in the modern and ancient records.We have used Black Sea sediments that are known to preserve enrichment and sedimentary isotope signatures for an Fe shuttle. This is due to an Fe transport from the more oxic margin to the deep euxinic basin and corresponding enrichment in the underlying sediments. These samples were used to test for a potential Fe and Mn shuttle effect on ε205Tl and δ51V in sediments deposited under oxic, suboxic, and euxinic water columns. Authigenic ε205Tl from all three depositional settings is indistinguishable (–2.7 ± 0.3, –2.4 ± 0.5, and –2.4 ± 0.3), which is within error of the Black Sea surface seawater (–2.2 ± 0.3). In contrast, oxic and suboxic sediment have similar δ51V values (–1.06 ± 0.33‰ and –1.04 ± 0.30‰), which are significantly more negative than euxinic sediments (–0.57 ± 0.06‰).All the sediments deposited under oxic, suboxic, and euxinic water columns in the Black Sea capture ε205Tl of the surface seawater because there is almost no permanent burial of Mn oxides in this basin. This finding is consistent with the indistinguishable ε205Tl between the surface seawater and the riverine input. Sedimentary δ51V appears to be controlled predominantly by the redox state of the depositional environments with little effect from an Fe or Mn shuttle. The lack of Fe and Mn shuttle effect on ε205Tl and δ51V in the Black Sea is likely due to the shallow (∼100 m) chemocline in the strongly, 2000-m deep redox-stratified water column of this basin and very slow deep-water renewal rate. Iron and Mn in oxides are not delivered to the sediments, instead, they are dissolved and captured in the water column as iron sulfide and reduced Mn mineral phases. Our results suggest that Fe and Mn shuttle transport mechanisms may not strongly affect Tl and V isotopes, at least in extreme cases of water column redox stratification. Further work is required to constrain the isotopic signals using other modern and, by inference, diverse ancient settings for additional shuttling mechanisms.