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.

Copper ecological risk assessment using DGT technique and PNEC: A case study in the Brazilian coast.

Estuarine systems are vulnerable to metals stress, such as copper (Cu). Thus, the development of applicable tools to improve routine monitoring programs is increasingly necessary. In the present work a comprehensive Ecological Risk Assessment (ERA) was implemented by coupling the Measured Environmental Concentration (MEC), based on labile Cu (DGT) and the total dissolved Cu concentration. Additionally, toxicity data related to site-specific Predicted No Effect Concentration (PNEC) were used. As case study, estuarine areas were selected on Brazilian coast, previously reported as Cu release in shipyard areas. The results indicated an increase in concentrations of dissolved and labile Cu during the application of antifouling paints. In locations where more vessels in maintenance were found, the concentration of Cu-DGT exceeded the PNEC value (0.16 µg.L-1) and represented an important part of the total dissolved fraction (>93 %). The MEC/PNEC quotients, showed that shipyard areas represent a high ecological risk. Thus, it is highlighted the need for site-specific environmental assessments to manage complex ecosystems and set in environmental legislation. Consequently, the novel coupling of DGT technique and the derivation of a site-specific PNEC represent an easily applicable tool as an alternative to classical ERAs.

Winter arsenic pollution in 10 forest ecosystems in the mountainous border regions of the Czech Republic.

Arsenic (As) concentrations and deposition fluxes were measured in snow and rime at 10 mountain-top sites near the borders between the Czech Republic and Austria, Germany, Poland, and Slovakia during three consecutive winter seasons (2009-2011). Our study was performed at a time following several decades of sharply decreasing regional atmospheric pollution and following the 2006 implementation of stricter air quality standards across Europe. Our objective was to compare vertical and horizontal depositions of soluble and insoluble As forms throughout the Czech Republic and define a recent Central European As pollution gradient. Arsenic soluble in weak nitric acid contributed 83 to 85% to the total As deposition, with the remaining 17-15% bound to stable particulate forms. The highest As deposition rates were recorded in the eastern Czech Republic near the borders with Poland and Slovakia. Complementary hydrochemical monitoring in four mountain-slope catchments situated near selected main study sites revealed a further decrease in open-area As deposition by the end of 2018 in the east of the country. In contrast, spruce canopy throughfall flux did not change significantly between 2009-2011 and 2016-2018. The site-specific relative roles of coal-burning-derived and ore-smelting-derived atmospheric As are discussed.

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.