Chemical speciation of chromium and nickel in the western Mediterranean

The chemical speciation of dissolved Cr and Ni was measured onboard ship in the western Mediterranean Sea using cathodic stripping voltammetry (CSV) during the winter of 1992 and summer of 1993. Vertical profiles for dissolved Cr(III) in the water column showed concentrations between 0 and 1.4 nM, with highest concentrations in the surface layer, possibly caused by photochemical conversion of Cr(VI) to Cr(III) during summer periods and by atmospheric inputs during winter periods. Enhanced Cr(III) levels also were encountered in the deeper Mediterranean waters and were attributed to mineralisation of sinking biological material and diffusion from sediments. Dissolved Cr(VI) concentrations ranged between 2 and 3 nM, and total dissolved Cr concentrations between 2 and 3.5 nM. Lowest concentrations of total Cr and Cr(VI) occurred in the surface Atlantic waters and highest levels in the deeper Mediterranean waters. Total dissolved Ni concentrations ranged between 1.5 and 5 nM. Between 10 and 20% of the total dissolved Ni in the western Mediterranean appeared to be strongly organically complexed. Both labile and total dissolved Ni concentrations were lower in the surface Atlantic waters than in the Mediterranean deeper waters. Little difference was observed between the data sets for winter and summer, indicating that the influence of seasonal changes on the speciation of Ni was small. A clear nutrient-like behaviour was not apparent for Ni and Cr, and their vertical and horizontal distributions were mainly determined by physical processes. Dissolved budget results for Cr and Ni for the Valdivia and Disco very (data in parentheses) cruises of -572 (55) and -439 (369) t yr(-1) were calculated, indicating that the dissolved budgets for these elements were well balanced. The budget deficits and surpluses for dissolved Cr and Ni were small compared to the mass fluxes involved in the calculation of the mass balances. (C) 1997 Elsevier Science Ltd.