Trace metal distributions in shelf waters of the northwestern Black Sea

Measurements of dissolved and leachable particulate trace metals (Mn, Fe, Co, Pb, Cd, Zn, Cu and Ni) and total particulate Mn and Fe were made on seawater samples collected from the northwestern Black Sea during the EROS 2000 expedition conducted in July-August 1995. The investigation concentrated on waters of the shelf and shelf edge, but included one deeper water (1440 m) station. In the oxic layer of the deep station, the suspended particulate fractions of Mn and Fe were a major part of the total metal mass, consistent with the presence of the ``Fine Particle Layer'' which forms on the shelf and spreads all over the Black Sea with intensities decreasing from the coast. Dissolved and total particulate concentrations were, respectively, Mn, 0.69-9.6, 1.2-29; Fe, 0.79-3.03, 2.3-7.4 nM. Dissolved Cu and Ni concentrations were relatively high (1-8 and 8-12 nM, respectively), and did not show any depletion in surface oxic waters, possibly as a result of strong organic complexation. Dissolved Pb concentrations (100-200 pM) were higher than were generally found on the shelf. This was attributed to atmospheric inputs combined with less efficient scavenging of metals in these low SPM waters. The distribution of dissolved Co closely resembled that of dissolved Mn reflecting coupling through oxidation of Mn. Concentrations of dissolved Cd and Zn were low in surface water (0.07-0.09 and 0.9-2.0 nM, respectively), and increases in concentrations with depth were sharply reversed around the top of the redoxcline. For most metals (Mn, Fe, Co, Pb, Cu, Cd, Zn) dissolved concentrations were low in the anoxic layers as a result of solubility by formation of, or association with, solid sulphide phases. Dissolved Ni was not affected by sulphide precipitation. At most of the shelf stations there were clear enhancements of dissolved Mn and Fe in the deepest waters, consistent with other evidence that significant benthic fluxes of these metals arise through the redox conditions in the region of the sediment-water interface. In the shelf water column, dissolved Mn and Fe concentrations ranged between 1.2 and 1350 and between 0.4 and 181 nM, respectively; the highest concentrations were found near the bottom. Particulate concentrations of Mn and Fe were high, implying high oxidation rates of Mn(II) and Fe(II) and/or high supply rates from rivers. Total particulate concentrations of Mn and Fe were 0.7-1050 and 2.3-2650 nM, respectively; the highest concentrations were found ill surface and bottom waters. The distributions of particulate Mn and Fe were consistent with the isopyenal transport or Mn and Fe oxyhydroxides from the shelf by the coastal circulation. Distributions of other trace metals (Co, Pb, Cu, Ni, Cd, Zn) were considerably influenced by riverine inputs. Relatively high dissolved and available particulate metal concentrations were generally found in surface waters at stations directly influenced by the Danube River. Some trace metals (Co, Ni, Cd and Zn) were influenced by Mn and Fe cycling and increases in their dissolved concentrations occurred at a number of stations near the sediment-water interface. Dissolved and available particulate metal concentrations (nM) at stations oil the shelf were, respectively: 0.171-1.80, 0.003-0.437 (Co); 0.014-0.614, 0.010-1.48 (Pb); 7.6-28.8, 0.048-3.75 (Cu); 11.0-17.5, 0.018-2.10 (Ni); 0.033-0.161, 0.003-0.063 (Cd); 1.01 8.33, 0.135 7.58 (Zn). (C) 2001 Elsevier Science Ltd. All rights reserved