Potential availability of trace metals in sediments in southeastern and southern Brazilian shipyard areas using the DGT technique and chemical extraction methods.

Speciation and partitioning of trace metals, from solid to solution phases of sediments, control their bioavailability and thus their potential ecological risk to organisms. Therefore, in order to obtain a broad evaluation of their risk, it is necessary to couple methodologies that are able to assess metal mobility in sediment. In this study, the Diffusive Gradients in Thin Films (DGT) technique and the application of 0.1 M HCl acid extraction methods, together with solid-state voltammetric sensors, were used with the objective of assessing mobility and potential availability of Cr, Cu, Ni, Pb, V and Zn in sediment porewaters and solid sediments in southeastern and southern Brazilian shipyard areas. The highest labile metal concentrations were found in shipyards with the longest histories of operations. Trace metal distributions in porewater and in the solid phase of sediments (labile metals) and significant correlations among metals enabled to distinguish the contribution of anti-fouling paint components. The diffusive flux of every metal measured at the surface of the sediment indicated that CuDGT had the highest flux (3.66E-03 mmol·m-2 d-1) in the shipyard with the longest operating time. Therefore, enrichment was observed for Cu, Pb and Zn in sediments, indicating a possible ecological risk level of 'Effects Range Median' to 'Apparent Effects Threshold' for oyster larvae (Mollusca) (Cu), bivalves (Pb) and the infaunal community (Zn). Probable Effect Concentrations (PEC) to sediment-dwelling biota can be expected as well, related to high concentrations of Cu and Zn in sediment. This study allowed a comprehensive evaluation of potential bioavailability and ecological risk of trace metals in aquatic systems where there is continuous and specific input of these elements. The use of the DGT technique with solid-state voltammetry in the sediment of distinct Brazilian estuarine systems demonstrated its potential to be applied in future environmental network programs.

Sulfide production and consumption in degrading wood in the marine environment.

Woody debris is known to be transported to the seas and accumulate on the seafloor, however, little is known on the consequences of its degradation in the marine environment. In this study we monitored the degradation product sulfide with Au/Hg voltammetric microelectrodes on the surface and interior of an experimentally immersed wood for 200 d. After 5 weeks of immersion, the interior became sulfidic, and steady-state conditions were established after 13 weeks with sulfide concentration reaching about 300 µM. Although sulfide was briefly detected at the surface of wood, its concentration remained lower than 20 µM, indicating that this compound was effectively oxidized within the substrate. Fitting these data to a kinetic model lead to an estimated microbial sulfide production rate in the range of 19-28 µM d(-1) at steady state. As much as 24 µM d(-1) nitrate could be consumed by this process in the steady-state period. Before the establishment of the steady state conditions, steep fluctuations in sulfide concentration (between 1mM and several µM) were observed in the wood interior. This study is the first to document the temporal dynamics of this unsteady process, characterized by fast sulfide fluctuation and consumption. Our results point to the complex mechanisms driving the dynamics of wood biogeochemical transformations, and reveal the capacity of woody debris to generate sulfidic conditions and act as a possible sink for oxygen and nitrate in the marine environment.