Ageing of copper, zinc and synthetic pesticides in particle-size and chemical fractions of agricultural soils.

The transformation and mobility of heavy metals and synthetic pesticides in soil depend on ageing, involving their chemical and physical distributions among soil fractions over time. Heavy metals and synthetic pesticides often co-occur in soil, although their ageing is usually evaluated separately and in bulk soil. Here, contrasting vineyard and crop soils were spiked with copper (Cu; 700 mg kg-1) and zinc (Zn; 200 mg kg-1) a and/or synthetic pesticides (5 mg kg-1), i.e., the fungicide metalaxyl (MTY) and herbicide S-metolachlor (SMET), to evaluate within 200 days their distribution among soil physical and chemical fractions. More than 90% of MTY and SMET in soil was released into the water phase, even 200 days after spiking. This emphasizes the potential mobilization of MTY and SMET from the soil following field application. MTY, SMET, Cu and Zn were associated mainly with the silt fraction and to a lesser extent (<30%) with the sand and clay fractions. Overall, the ageing of MTY, SMET, Cu and Zn in agricultural soil was affected mainly by the soil type and sterilization and only to a minor extent by their co-occurrence. Sorption controlled the dissipation of MTY and SMET in soil, while biodegradation contributed to less than 10%. A large fraction (37 ± 2%) of Cu was associated with Fe oxides after 200 days of ageing, while Zn was found (33 ± 2%) in the residual soil fraction. The silt fraction of the nonsterile vineyard soil became enriched in 65Cu over time (Δδ65Cu = 0.25 ± 0.07‰), whereas the clay fraction was depleted in 65Cu (Δδ65Cu = -0.20 ± 0.07‰). Cu isotope fractionation mirrored the Cu distribution in soil chemical fractions, suggesting that Cu stable isotopes may help to follow-up Cu ageing. In contrast, no significant Zn isotope fractionation was observed among soil experiments or over time. Overall, our study emphasizes the variability in ageing of synthetic pesticides and heavy metals co-occurring in agricultural soils and their interplay in physical and chemical fractions of the soil.

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.