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

Abstract

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.

Assessment of the metal contamination evolution in the Loire estuary using Cu and Zn stable isotopes and geochemical data in sediments

“…Trace metals are released by anthropogenic activities (e.g. agriculture, industry, mining, metallurgy, energy production and transport) and dispersed among the different natural compartments such as the soil (Babcsányi et al, 2016;Bigalke et al, 2010;Fekiacova et al, 2015a;Juillot et al, 2011), the water (Araújo et al, 2017a;Borrok et al, 2008;Chen et al, 2008;Skierszkan et al, 2016;Thapalia et al, 2015) and the atmosphere (Dong et al, 2017;Gonzalez et al, 2016;Novak et al, 2016;Souto-Oliveira et al, 2018). To develop correct environmental management strategies, either for remediation actions appropriately targeted as well as to maintain emissions at sustainable levels, it is imperative to identify their sources, to understand their transport and fates in the environment and to examine at what extent the anthropogenic activities affect their biogeochemical cycling.…”

“…In surface environments, the relative abundance of these isotopes can change during several biogeochemical processes including weathering and pedogenesis (Bigalke et al, 2011;Fernandez and Borrok, 2009;Suhr et al, 2018;Vance et al, 2016), mineral precipitation/dissolution (Veeramani et al, 2015;Wall et al, 2011), adsorption on solid surfaces (Bryan et al, 2015;Dong and Wasylenki, 2016;Guinoiseau et al, 2016), ion-exchange (Maréchal and Albarède, 2002), cellular homeostasis (Caldelas et al, 2011;Wanty et al, 2017), redox reactions and ore refining (smelting and electroplating, (Kavner et al, 2008;Sivry et al, 2008a;Sonke et al, 2002;Yin et al, 2018Yin et al, , 2015. The different mechanisms of Cu and Zn isotope fractionation, e.g, via kinetic or thermodynamic equilibrium, and the significant isotopic signature variability observed among different natural compartments and materials, enable these isotopes to be potential environmental indicators useful to detect trends of pollution over time periods, identifying sources of contamination and elucidate contaminant transport mechanisms (Babcsányi et al, 2016;El Azzi et al, 2013;Petit et al, 2015;Sivry et al, 2008;Thapalia et al, 2015).…”

“…We expect that spatial and temporal patterns of trace metal concentrations coupled to Cu and Zn isotope ratios on sediments can be useful to deconvolve past and current anthropogenic inputs to the estuarine system. Copper is redox sensitive and widely used as a component of agricultural fungicides (Babcsányi et al, 2016(Babcsányi et al, , 2014El Azzi et al, 2013), while Zn is redox-insensitive and a contaminant frequently associated to urban and industrial contamination (Chen et al, 2009;Souto-Oliveira et al, 2018).…”

Copper, zinc and lead isotope signatures of sediments from a mediterranean coastal bay impacted by naval activities and urban sources

“…Since anthropogenic Cu may derive either from sulfides or oxide ore deposits, Cu isotope systematics can help discriminate the different anthropogenic and natural sources. In environmental studies, Cu isotopes have been a useful tracer in urban aerosol samples (Souto-Oliveira et al, 2019 and in surrounding soils impacted by metallurgical (Mihaljevič et al, 2019;Šillerová et al, 2017) and vineyard activities (Babcsányi et al, 2016;El Azzi et al, 2013), however their applicability in complex and reactive aquatic systems has been more challenging (Araújo et al, 2019;Petit et al, 2013;Viers et al, 2018).…”

RECOTOX, a French initiative in ecotoxicology-toxicology to monitor, understand and mitigate the ecotoxicological impacts of pollutants in socioagroecosystems

“…A specificity of the catchment is that it enables to investigate the plot–catchment–wetland buffer zone continuum (Imfeld et al 2013 ). Among other things, it also enables to study the phytoremediation and organic (Maillard and Imfeld 2014 ) and inorganic (copper and zinc, Babcsányi et al 2016 ) pesticide degradation potential of the stormwater wetland. The QUASAPROVE network ( http://www.quasaprove.org/moodle/ ) is an observatory devoted to the study of diffuse contamination of crop fields by mycotoxins, trace elements, and pesticide residues.…”