Ecological risk and enrichment of potentially toxic elements in the soil and eroded sediment in an organic vineyard (Tokaj Nagy Hill, Hungary).

Potentially toxic elements (PTEs), such as Cu, Zn, Pb, Ni, Cr, and Co, can accumulate in vineyard soils due to repeated uses of inorganic pesticides and chemical or organic fertilizers. In sloping vineyards, PTEs can also be moved by soil erosion resulting in their accumulation in low-energy zones within the landscape, adversely affecting the soil environment. Our study evaluated the ecological risk related to the pseudo-total and bioavailable PTE contents (Zn, Pb, Co, Ni, Cr, and Cu) in the soil and eroded sediment samples from an organic vineyard in Tokaj (NE Hungary). The contamination status and the ecological risk of target PTEs were assessed by calculating the contamination factor, the pollution load index, the ecological risk factor, and the ecological risk index. The median pollution load indices of 1.15, 1.81, and 1.10 for the topsoil, the sediments, and the subsoil, respectively, demonstrate a moderate multi-element contamination case in the organic vineyard. Target PTEs tented to show increased concentrations in eroded sediments with the highest enrichment ratio (3.36) observed for Cu (Cu in the sediment/Cu in the topsoil), revealing a preferential movement of Cu-rich soil particles by overland flow. Moreover, PTEs were present in the sediments in more bioavailable forms (except Ni, Cr), assessed by an extraction procedure with EDTA. The ecological risk index (< 90) based on the studied PTEs showed an overall low ecological risk in the vineyard. Copper was the predominant factor of the ecological risk. Moreover, the highest ecological risk factor (24.6) observed for the bioavailable Cu content in an eroded sediment sample (representing 82% of the total ecological risk) shows that Cu accumulation in sloping vineyards is an ecological risk, particularly in the sedimentation zones. The high proportions of bioavailable Cu in the vineyard's soil represent an increasing ecological risk over time, related to repeated treatments of vine plants with Cu-based pesticides.

Biogeochemical gradients and microbial communities in Winogradsky columns established with polluted wetland sediments.

A Winogradsky column is a miniature ecosystem established with enriched sediments that can be used to study the relationship between biogeochemical gradients, microbial diversity and pollutant transformation. Biogeochemical processes and microbial communities changed with time and depth in Winogradsky columns incubated with heavy-metal-polluted wetland sediments for 520 days. 16S rRNA surveys were complemented by geochemical analyses, including heavy metal proportioning, to evaluate gradients in the mostly anoxic columns. Oxygen was depleted below the water-sediment interface (WSI), while NH4+, Fe2+, S2- and acetate increased by one order of magnitude at the bottom. Microbial niche differentiation occurred mainly by depth and from the light-exposed surface to the interior of the columns. Chemical gradients resulting from nutrient uptake by algae, and from iron and sulphate reduction mainly drove diversification. Heavy-metal proportioning did not significantly influence microbial diversity as Cu and Zn were immobilised at all depths. Proteobacteria were abundant in the top water and the WSI layers, whereas Firmicutes and Bacteroida dominated down-core. Together with low diversity and richness of communities at the WSI and column bottom, changes in the bacterial community coincided with algal-derived carbon sources and cellulose fermentation, respectively. We expect this study to be the starting point for the use Winogradsky columns to study microbial and geochemical dynamics in polluted sediments.

Copper in soil fractions and runoff in a vineyard catchment: Insights from copper stable isotopes.

Understanding the fate of copper (Cu) fungicides in vineyard soils and catchments is a prerequisite to limit the off-site impact of Cu. Using Cu stable isotopes, Cu retention in soils and runoff transport was investigated in relation to the use of Cu fungicides and the hydrological conditions in a vineyard catchment (Rouffach, Haut-Rhin, France; mean slope: 15%). The δ(65)Cu values of the bulk vineyard soil varied moderately through the depth of the soil profiles (-0.12 to 0.24‰±0.08‰). The values were in the range of those of the fungicides (-0.21 to 0.11‰) and included the geogenic δ(65)Cu value of the untreated soil (0.08‰). However, δ(65)Cu values significantly differed between particle-size soil fractions (-0.37±0.10‰ in fine clays and 0.23±0.07‰ in silt). Together with the soil mineralogy, the results suggested Cu isotope fractionation primarily associated with the clay and fine clay fractions that include both SOM and mineral phases. The vegetation did not affect the Cu isotope patterns in the vineyard soils. Cu export by runoff from the catchment accounted for 1% of the applied Cu mass from 11th May to 20(th) July 2011, covering most of the Cu use period. 84% of the exported Cu mass was Cu bound to suspended particulate matter (SPM). The runoff displayed δ(65)Cu values from 0.52 to 1.35‰ in the dissolved phase (<0.45µm) compared to -0.34 to -0.02‰ in the SPM phase, indicating that clay and fine clay fractions were the main vectors of SPM-bound Cu in runoff. Overall, this study shows that Cu stable isotopes may allow identifying the Cu distribution in the soil fractions and their contribution to Cu export in runoff from Cu-contaminated catchments.

Copper stable isotopes to trace copper behavior in wetland systems.

Wetlands are reactive zones of the landscape that can sequester metals released by industrial and agricultural activities. Copper (Cu) stable isotope ratios (δ(65)Cu) have recently been used as tracers of transport and transformation processes in polluted environments. Here, we used Cu stable isotopes to trace the behavior of Cu in a stormwater wetland receiving runoff from a vineyard catchment (Alsace, France). The Cu loads and stable isotope ratios were determined in the dissolved phase, suspended particulate matter (SPM), wetland sediments, and vegetation. The wetland retained >68% of the dissolved Cu and >92% of the SPM-bound Cu, which represented 84.4% of the total Cu in the runoff. The dissolved Cu became depleted in (65)Cu when passing through the wetland (Δ(65)Cuinlet-outlet from 0.03‰ to 0.77‰), which reflects Cu adsorption to aluminum minerals and organic matter. The δ(65)Cu values varied little in the wetland sediments (0.04 ± 0.10‰), which stored >96% of the total Cu mass within the wetland. During high-flow conditions, the Cu flowing out of the wetland became isotopically lighter, indicating the mobilization of reduced Cu(I) species from the sediments and Cu reduction within the sediments. Our results demonstrate that the Cu stable isotope ratios may help trace Cu behavior in redox-dynamic environments such as wetlands.