Labile metal assessment in water by diffusive gradients in thin films in shipyards on the Brazilian subtropical coast

Shipyards impact on estuarine environments because of the use of antifouling paints and petroleum products, which release trace metals that may remain in their bioavailable or labile form. Regardless of its importance, the relation between continuous input of trace metals (hotspot area) and their availability in the water column has been scarcely studied. This study evaluated seasonal variations in the concentrations of labile fractions of metals in shipyards located in estuarine areas on the Brazilian subtropical coast. These fractions were determined by the Diffuse Gradients in Thin Films (DGT) technique. Maximum labile fraction concentrations of Cr (0.3 μg L−1), Ni (2.2 μg L−1) and V (2.0 μg L−1) are directly related to (i) their specific source: antifouling paints (for Cr), metal and steel alloys (for Cr and Ni) and petroleum products (for V), besides (ii) periods of intensive traffic and vessel repair. Additionally, variations in labile fractions of Ni and V in the Patos Lagoon estuary were influenced by salinity, which is known to affect metal desorption from surface sediments in resuspension events. Even though Cr is affected by the same processes, it is available as Cr(III) and does not represent any ecological risk in the study areas. Although the areas under study are affected by variations in physical and chemical conditions, shipyards were effectively hotspots of trace metals in their labile fraction in various estuarine systems in southeastern and southern Brazil. Thus, they represent areas where Ecological Risk Assessment, mainly of V, should be carried out

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 CU DGT 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