Stable isotope composition of pesticides in commercial formulations: The ISOTOPEST database.

By assessing the changes in stable isotope compositions within individual pesticide molecules, Compound Specific Isotope Analysis (CSIA) holds the potential to identify and differentiate sources and quantify pesticide degradation in the environment. However, the environmental application of pesticide CSIA is limited by the general lack of knowledge regarding the initial isotopic composition of active substances in commercially available formulations used by farmers. To address this limitation, we established a database aimed at cataloguing and disseminating isotopic signatures in commercial formulations to expand the use of pesticide CSIA. Our study involved the collection of 25 analytical standards and 120 commercial pesticide formulations from 23 manufacturers. Subsequently, 59 commercial formulations and 25 standards were extracted, and each of their active substance was analyzed for both δ13C (n = 84) and δ15N CSIA (n = 43). The extraction of pesticides did not cause significant isotope fractionation (Δ13C and Δ15N < 1‰). Incorporating existing literature data, stable carbon and nitrogen isotope signatures varied in a relatively narrow range among pesticide formulations for different pesticides (Δ13C and Δ15N < 10‰) and within different formulations for a single substance (Δ13C and Δ15N < 2‰). Overall, this suggests that pesticide CSIA is more suited for identifying pesticide transformation processes rather than differentiating pesticide sources. Moreover, an inter-laboratory comparison showed similar δ13C (Δ13C ≤ 1.2 ‰) for the targeted substances albeit varying GC-IRMS instruments. Insignificant carbon isotopic fractionation (Δ13C < 0.5‰) was observed after 4 years of storing the same pesticide formulations, confirming their viability for long-term storage at 4 °C and future inter-laboratory comparison exercises. Altogether, the ISOTOPEST database, in open access for public use and additional contributions, marks a significant advancement in establishing an environmentally relevant pesticide CSIA approach.

Emissions of the Urban Biocide Terbutryn from Facades: The Contribution of Transformation Products.

Biocides are added to facade paints and renders to prevent algal and fungal growth. The emissions of biocides and their transformation products from building facades during wind-driven rain can contaminate surface waters, soil, and groundwater. Although the emissions of biocide transformation products may be higher than those of the parent biocide, knowledge of the emissions of transformation products over time is scarce. Combining field- and lab-scale experiments, we showed that solar irradiation on facades controls the formation of transformation products and can be used with runoff volume to estimate the long-term emissions of terbutryn transformation products from facades. The slow (t1/2 > 90 d) photodegradation of terbutryn in paint under environmental conditions was associated with insignificant carbon isotope fractionation (Δδ13C < 2 ‰) and caused 20% higher emission of terbutryn-sulfoxide than terbutryn in leachates from facades. This indicated continuous terbutryn diffusion toward the paint surface, which favored terbutryn photodegradation and the concomitant formation of transformation products over time. The emissions of terbutryn transformation products (77 mg m-2) in facade leachates, modeled based on irradiation and facade runoff, were predicted to exceed those of terbutryn (42 mg m-2) by nearly 2-fold after eight years. Overall, this study provides a framework to estimate and account for the long-term emissions of biocide transformation products from building facades to improve the assessment of environmental risks.

Evaluating pesticide degradation in artificial wetlands with compound-specific isotope analysis: A case study with the fungicide dimethomorph.

Pesticide degradation in wetland systems intercepting agricultural runoff is often overlooked and mixed with other dissipation processes when assessing pesticide concentrations alone. This study focused on the potential of compound-specific isotope analysis (CSIA) to estimate pesticide degradation in a stormwater wetland receiving pesticide runoff from a vineyard catchment. The fungicide dimethomorph (DIM), with diastereoisomers E and Z, was the prevalent pesticide in the runoff entering the wetland from June to September 2020. DIM Z, the most commonly detected isomer, exhibited a significant change (Δ(13C) > 3 ‰) in its carbon isotopic composition in the wetland water compared to the runoff and commercial formulation, which indicated degradation. Laboratory DIM degradation assays, including photodegradation and biodegradation in oxic wetland water with and without aquatic plants and in anoxic sediments, indicated that DIM degradation mainly occurred in the wetland sediments. The rapid degradation of both DIM isomers (E:t1/2 = 1.2 ± 0.6, Z: t1/2 = 1.5 ± 0.8 days) in the wetland sediment led to significant carbon isotopic fractionation (εDIM-E = -3.0 ± 0.6 ‰, εDIM-Z = -2.0 ± 0.2 ‰). In contrast, no significant isotope fractionation occurred during DIM photodegradation, despite the rapid isomerization of the E isomer to the Z isomer and a half-life of 15.3 ± 2.2 days for both isomers. DIM degradation was slow (E: t1/2 = 56-62 days, Z: t1/2 = 82-103 days) in oxic water with plants, while DIM persisted (120 days) in water without plants. DIM CSIA was thus used to evaluate the in situ biodegradation of DIM Z in the wetland. The DIM Z degradation estimates based on a classical concentration mass balance (86-94 %) were slightly higher than estimates based on the isotopic mass balance (61-68 %). Altogether, this study shows the potential of CSIA to conservatively evaluate pesticide degradation in wetland systems, offering a reliable alternative to classical labor-intensive mass balance approaches.).

Dimethomorph degradation in vineyards examined by isomeric and isotopic fractionation.

Knowledge of the degradation extent and pathways of fungicides in the environment is scarce. Fungicides may have isomers with distinct fungal-control efficiency, toxicity and fate in the environment, requiring specific approaches to follow up the degradation of individual isomers. Here we examined the degradation of the widely used fungicide dimethomorph (DIM) in a vineyard catchment using ratios of carbon stable isotopes (δ13C) and E/Z isomer fractionation (IF(Z)). In a microcosm laboratory experiment, DIM degradation half-life in soil was 20 ± 3 days, and was associated with significant isomeric (ΔIF(Z) = +30%) and isotopic (Δδ13C up to 7‰) fractionation. This corresponds to an isomer enrichment factor of εIR = -54 ± 6%, suggesting isomer selectivity and similar carbon stable isotopic fractionation values of εDIM-(Z) = -1.6 ± 0.2‰ and εDIM-(E) = -1.5 ± 0.2‰. Isomeric and isotopic fractionation values were used to estimate DIM degradation in topsoil and transport in a vineyard catchment over two wine-growing seasons. DIM concentrations following DIM application were up to 3 µg g-1 in topsoil and 29 µg L-1 in runoff water at the catchment outlet. Accordingly, the IF(Z) and δ13C values of DIM in soil were similar to those observed in DIM commercial formulations. The gradual enrichments in DIM-(Z) and 13C of the residual DIM in soil indicated DIM biodegradation over time. DIM biodegradation estimated based on E/Z isomer and carbon stable isotope ratios in topsoil and runoff water ranged from 0% after DIM application up to 100% at the end of the wine-growing season. DIM biodegradation was overestimated compared to conventional approaches relying on DIM mass balance, field concentrations and half-lives. Altogether, our study highlights the usefulness of combining carbon stable isotopes, E/Z isomers and classical approaches to estimate fungicide degradation at the catchment scale, and uncovers difficulties in using laboratory-derived values in field studies.

Do pesticides degrade in surface water receiving runoff from agricultural catchments? Combining passive samplers (POCIS) and compound-specific isotope analysis.

Pesticides lead to surface water pollution and ecotoxicological effects on aquatic biota. Novel strategies are required to evaluate the contribution of degradation to the overall pesticide dissipation in surface waters. Here, we combined polar organic chemical integrative samplers (POCIS) with compound-specific isotope analysis (CSIA) to trace in situ pesticide degradation in artificial ponds and agricultural streams. The application of pesticide CSIA to surface waters is currently restricted due to environmental concentrations in the low µg.L-1 range, requiring processing of large water volumes. A series of laboratory experiments showed that POCIS enables preconcentration and accurate recording of the carbon isotope signatures (δ13C) of common pesticides under simulated surface water conditions and for various scenarios. Commercial and in-house POCIS did not significantly (Δδ13C < 1 %) change the δ13C of pesticides during uptake, extraction, and δ13C measurements of pesticides, independently of the pesticide concentrations (1-10 µg.L-1) or the flow speeds (6 or 14 cm.s-1). However, simulated rainfall events of pesticide runoff affected the δ13C of pesticides in POCIS. In-house POCIS coupled with CSIA of pesticides were also tested under different field conditions, including three flow-through and off-stream ponds and one stream receiving pesticides from agricultural catchments. The POCIS-CSIA method enabled to determine whether degradation of S-metolachlor and dimethomorph mainly occurred in agricultural soil or surface waters. Comparison of δ13C of S-metolachlor in POCIS deployed in a stream with δ13C of S-metolachlor in commercial formulations suggested runoff of fresh S-metolachlor in the midstream sampling site, which was not recorded in grab samples. Altogether, our study highlights that the POCIS-CSIA approach represents a unique opportunity to evaluate the contribution of degradation to the overall dissipation of pesticides in surface waters.

Transformation and stable isotope fractionation of the urban biocide terbutryn during biodegradation, photodegradation and abiotic hydrolysis.

Terbutryn is a widely used biocide in construction materials like paint and render to prevent the growth of microorganisms, algae and fungi. Terbutryn is released from the facades into the environment during rainfall, contaminating surface waters, soil and groundwater. Knowledge of terbutryn dissipation from the facades to aquatic ecosystems is scarce. Here, we examined in laboratory microcosms degradation half-lives, formation of transformation products and carbon and nitrogen isotope fractionation during terbutryn direct (UV light with λ = 254 nm and simulated sunlight) and indirect (simulated sunlight with nitrate) photodegradation, abiotic hydrolysis (pH = 1, 7 and 13), and aerobic biodegradation (stormwater pond sediment, soil and activated sludge). Biodegradation half-lives of terbutryn were high (>80 d). Photodegradation under simulated sunlight and hydrolysis at extreme pH values indicated slow degradability and accumulation in the environment. Photodegradation resulted in a variety of transformation products, whereas abiotic hydrolysis lead solely to terbutryn-2-hydroxy in acidic and basic conditions. Biodegradation indicates degradation to terbutryn-2-hydroxy through terbutryn-sulfoxide. Compound-specific isotope analysis (CSIA) of terbutryn holds potential to differentiate degradation pathways. Carbon isotope fractionation values (εC) ranged from -3.4 ± 0.3‰ (hydrolysis pH 1) to +0.8 ± 0.1‰ (photodegradation under UV light), while nitrogen isotope fractionation values ranged from -1.0 ± 0.4‰ (simulated sunlight photodegradation with nitrate) to +3.4 ± 0.2‰ (hydrolysis at pH 1). In contrast, isotope fractionation during biodegradation was insignificant. ΛN/C values ranged from -1.0 ± 0.1 (hydrolysis at pH 1) to 2.8 ± 0.3 (photodegradation under UV light), allowing to differentiate degradation pathways. Combining the formation of transformation products and stable isotope fractionation enabled identifying distinct degradation pathways. Altogether, this study highlights the potential of CSIA to follow terbutryn degradation in situ and differentiate prevailing degradation pathways, which may help to monitor urban biocide remediation and mitigation strategies.

Direct and indirect photodegradation of atrazine and S-metolachlor in agriculturally impacted surface water and associated C and N isotope fractionation.

Knowledge of direct and indirect photodegradation of pesticides and associated isotope fractionation can help to assess pesticide degradation in surface waters. Here, we investigated carbon (C) and nitrogen (N) isotope fractionation during direct and indirect photodegradation of the herbicides atrazine and S-metolachlor in synthetic agriculturally impacted surface waters containing nitrates (20 mg L-1) and dissolved organic matter (DOM, 5.4 mgC L-1). Atrazine and S-metolachlor were quickly photodegraded by both direct and indirect processes (half-lives <5 and <7 days, respectively). DOM slowed down photodegradation while nitrates increased degradation rates. The analysis of transformation products showed that oxidation mediated by hydroxyl radicals (HO˙) predominated during indirect photodegradation. UV light (254 nm) led to significant C and N isotope fractionation, yielding isotopic fractionation values εC = 2.7 ± 0.3 and 0.8 ± 0.1‰, and εN = 2.4 ± 0.3 and -2.6 ± 0.7‰ for atrazine and S-metolachlor, respectively. In contrast, photodegradation under simulated sunlight led to negligible C and slight N isotope fractionation, emphasizing the effect of the radiation wavelengths on the isotope fractionation induced by direct photodegradation. Altogether, these results highlight the importance of using simulated sunlight to obtain environmentally-relevant isotopic fractionation values and to distinguish photodegradation and other dissipation pathways in surface waters.

Copper Content and Export in European Vineyard Soils Influenced by Climate and Soil Properties.

Copper-based fungicides (Cuf) are used in European (EU) vineyards to prevent fungal diseases. Soil physicochemical properties locally govern the variation of the total copper content (Cut) in EU vineyards. However, variables controlling Cut distribution at a larger scale are poorly known. Here, machine learning techniques were used to identify governing variables and to predict the Cut distribution in EU vineyards. Precipitation, aridity and soil organic carbon are key variables explaining together 45% of Cut distribution across EU vineyards. This underlines the effect of both climate and soil properties on Cut distribution. The average net export of Cu at the EU scale is 0.29 kg Cu ha-1, which is 2 orders of magnitude less than the net accumulation of Cu (24.8 kg Cu ha-1). Four scenarios of Cuf application were compared. The current EU regulation with a maximum of 4 kg Cu ha-1 year-1 may increase by 2% of the EU vineyard area, exceeding the predicted no-effect concentration (PNEC) in soil in the next 100 years. Overall, our results highlight the vineyard areas requiring specific remediation measures and strategies of Cuf use to manage a trade-off between pest control and soil and water contamination.

Phase Transfer and Biodegradation of Pesticides in Water-Sediment Systems Explored by Compound-Specific Isotope Analysis and Conceptual Modeling.

Current approaches are often limited to evaluating the contribution of pesticide dissipation processes in water-sediment systems as both degradation and phase transfer, that is, sorption-desorption, contribute to the apparent decrease of pesticide concentration. Here, the dissipation of widely used herbicides acetochlor and S-metolachlor was examined in laboratory by water-sediment microcosm experiments under oxic and anoxic conditions. Compound-specific isotope analysis (CSIA) emphasized insignificant carbon isotope fractionation in the sediment, indicating prevailing pesticide degradation in the water phase. Conceptual modeling accounting for phase transfer and biodegradation indicated that biodegradation may be underestimated when phase transfer is not included. Phase transfer does not affect carbon isotope fractionation for a wide spectrum of molecules and environmental conditions, underscoring the potential of pesticide CSIA as a robust approach to evaluate degradation in water-sediment systems. CSIA coupled with the identification of transformation products by high-resolution tandem mass spectrometry suggests the degradation of acetochlor and S-metolachlor to occur via nucleophilic substitution and the predominance of oxalinic acids as transformation products under both anoxic and oxic conditions. Altogether, combining the pesticide CSIA, the identification of transformation products, and the use of conceptual phase-transfer models improves the interpretation of pesticide dissipation in water-sediment systems.

Do rainfall characteristics affect the export of copper, zinc and synthetic pesticides in surface runoff from headwater catchments?

Rainfall and runoff characteristics may influence off-site export of pesticides into downstream aquatic ecosystems. However, the relationship between rainfall characteristics and pesticide export from small headwater catchments remains elusive due to confounding factors including the application dose and timing and the variation of pesticide stocks in soil. Here we examined the impact of rainfall characteristics on the export of copper (Cu), zinc (Zn) and 12 legacy and currently used synthetic pesticides in surface runoff from a headwater vineyard catchment. Cluster analysis of rainfall intensity, depth and duration of 78 events revealed four distinct rainfall categories, i.e., Small, Long, Moderate and Intense (p < 0.001). Event mean concentrations of pesticides did not differ among rainfall categories (p > 0.05). In contrast, event loads of both dissolved and solid-bound Cu and Zn significantly differed among rainfall categories (p < 0.001). Rainfall depth and intensity significantly correlated with both Cu and Zn loads in runoff (ρs = 0.33 to 0.92, p < 0.002), and might be the main drivers of Cu and Zn export at the catchment scale. In contrast, rainfall depth, intensity or duration did not influence the loads of synthetic pesticides in runoff, even when weekly variations of pesticide stocks in the soil were accounted for. However, intense rainfall-runoff events, that can fragment soil, may control the export of persistent and hydrophobic legacy pesticides stocks in the soil, such as simazine and tetraconazole. Our results show that rainfall characteristics controlled the off-site export of Cu, Zn and legacy synthetic pesticides in a small headwater catchment, whereas the application timing drove the export of currently used synthetic pesticides in runoff. We anticipate our results to be a preliminary step to forecast the influence of regional rainfall patterns on the export of both metallic and synthetic pesticides by surface runoff from small agricultural headwater catchments.

Fungicides: An Overlooked Pesticide Class?

Fungicides are indispensable to global food security and their use is forecasted to intensify. Fungicides can reach aquatic ecosystems and occur in surface water bodies in agricultural catchments throughout the entire growing season due to their frequent, prophylactic application. However, in comparison to herbicides and insecticides, the exposure to and effects of fungicides have received less attention. We provide an overview of the risk of fungicides to aquatic ecosystems covering fungicide exposure (i.e., environmental fate, exposure modeling, and mitigation measures) as well as direct and indirect effects of fungicides on microorganisms, macrophytes, invertebrates, and vertebrates. We show that fungicides occur widely in aquatic systems, that the accuracy of predicted environmental concentrations is debatable, and that fungicide exposure can be effectively mitigated. We additionally demonstrate that fungicides can be highly toxic to a broad range of organisms and can pose a risk to aquatic biota. Finally, we outline central research gaps that currently challenge our ability to predict fungicide exposure and effects, promising research avenues, and shortcomings of the current environmental risk assessment for fungicides.

Carbon and nitrogen stable isotope fractionation during abiotic hydrolysis of pesticides.

Compound-specific Stable Isotope Analysis (CSIA) has been recently established as a tool to study pesticide degradation in the environment. Among degradative processes, hydrolysis is environmentally relevant as it can be chemically or enzymatically mediated. Here, CSIA was used to examine stable carbon and nitrogen isotope fractionation during abiotic hydrolysis of legacy or currently used pesticides (chloroacetanilide herbicides: Acetochlor, Alachlor, S-Metolachlor and Butachlor, acylalanine fungicide: Metalaxyl, and triazine herbicide: Atrazine). Degradation products analysis and CN dual-CSIA allowed to infer hydrolytic degradation pathways from carbon and nitrogen isotopic fractionation. Carbon isotopic fractionation for alkaline hydrolysis revealed similar apparent kinetic isotope effects (AKIEC = 1.03-1.07) for the 6 pesticides, which were consistent with SN2 type nucleophilic substitutions. Neither enantio-selectivity (EF ≈ 0.5) nor enantio-specific isotope fractionation occurred during hydrolysis of R (AKIEC = 1.04 ±â€¯0.01) and S (AKIEC = 1.04 ±â€¯0.02) enantiomers of a racemic mixture of Metalaxyl. Dual element isotope plots enabled to tease apart CCl bond breaking of alkane (Λ ≈ εN/εC ≈ 0, Acetochlor, Butachlor) and aromatic π-system (Λ ≈ 0.2, Atrazine) from CO bond breaking by dealkylation (Λ ≈ 0.9, Metalaxyl). Reference values for abiotic versus biotic SN2 reactions derived from carbon and nitrogen CSIA may be used to untangle pesticide degradation pathways and evaluate in situ degradation during natural and engineered remediation.

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

RECOTOX is a cross-cutting initiative promoting an integrated research to respond to the challenges of monitoring, understanding, and mitigating environmental and health impacts of pesticides in agroecosystems. The added value of RECOTOX is to develop a common culture around spatial ecotoxicology including the whole chain of pressure-exposure-impact, while strengthening an integrated network of in natura specifically equipped sites. In particular, it promotes transversal approaches at relevant socioecological system scales, to capitalize knowledge, expertise, and ongoing research in ecotoxicology and, to a lesser extent, environmental toxicology. Thus, it will open existing research infrastructures in environmental sciences to research programs in ecotoxicology of pesticides.

Pesticide degradation and export losses at the catchment scale: Insights from compound-specific isotope analysis (CSIA).

Although pesticides undergo degradation tests prior to use, determining their export, degradation and persistence under field conditions remains a challenge for water resource management. Compound specific isotope analysis (CSIA) can provide evidence of contaminant degradation extent, as it is generally independent of non-destructive dissipation (e.g., dilution, sorption, volatilization) regulating environmental concentrations. While this approach has been successfully implemented in subsurface environments, its application to pesticides in near-surface hydrological contexts at catchment scale is lacking. This study demonstrates the applicability of CSIA to track pesticide degradation and export at catchment scale and identify pesticide source areas contributing to changes in stable isotope signature in stream discharge under dynamic hydrological contexts. Based on maximum shifts in carbon stable isotope signatures (Δδ13C  = 4.6 ± 0.5‰) of S-metolachlor (S-met), a widely used herbicide, we estimate maximum degradation to have reached 96 ± 3% two months after first application. Maximum shifts in nitrogen isotope signatures were small and inverse (Δδ15N=-1.3±0.6‰) indicating potential secondary isotope effects during degradation. In combination with a mass balance approach including S-met main degradation products, total catchment non-destructive dissipation was estimated to have reached 8 ± 7% of the applied product. Our results show that CSIA can be applied to evaluate natural attenuation of pesticides at catchment scale. By providing a more detailed account of pesticide dissipation and persistence under field conditions we anticipate the contribution of pesticide CSIA to the improvement of regulatory and monitoring strategies.

Fluorescent tracers to evaluate pesticide dissipation and transformation in agricultural soils.

This study evaluates the mobility and dissipation of two organic fluorescent tracers (uranine, UR and sulforhodamine-B, SRB) in soil from an agricultural field. Two plot experiments were conducted for 2.5months in 2012 and 2016 to compare the behavior of reactive fluorescent tracers (UR and SRB) to the chloroacetanilide herbicide S-metolachlor (S-MET) and bromide (BR), used as a traditional conservative tracer. SRB in top soil closely mimicked the gradual recession of S-MET, while BR overrated both top soil mobility and slow leaching of S-MET in the soil column. In contrast, UR quickly receded in the soil and was entirely dissipated at the end of the study periods. Instead, a strong fluorescent signal that was stable against acidification, and non-traceable in background samples, gradually developed at an excitation wavelength of 510nm in samples from the uppermost soil layer starting 40 (2012) and 22 (2016) days after tracer application. We hypothesize that (bio-)chemical transformation of UR accelerated tracer loss with concomitant formation of the specific transformation product TP510. By LC-MS/MS analysis we propose a probable molecular structure of TP510 and sulfonation as one likely transformation process. Overall, we anticipate our results to be a starting point to use fluorescent tracers in longer term (>2months) agricultural soil studies as a proxy for S-MET and possibly also other organic pesticides, as they are non-conservative in unsaturated soil and may follow similar dissipation and transformation patterns. At the same time their analysis is less costly and they pose smaller environmental risks.

Impact of rainfall patterns and frequency on the export of pesticides and heavy-metals from agricultural soils.

The combined influence of soil characteristics, pollutant aging and rainfall patterns on the export of pollutants from topsoils is poorly understood. We used laboratory experiments and parsimonious modeling to evaluate the impact of rainfall characteristics on the ponding and the leaching of a pollutant mixture from topsoils. The mixture included the fungicide metalaxyl, the herbicide S-metolachlor, as well as copper (Cu) and zinc (Zn). Four rainfall patterns, which differed in their durations and intensities, were applied twice successively with a 7days interval on each soil type. To evaluate the influence of soil type and aging, experiments included crop and vineyard soils and two stages of pollutant aging (0 and 10days). The global export of pollutants was significantly controlled by the rainfall duration and frequency (P<0.01). During the first rainfall event, the longest and most intense rainfall pattern yielded the largest export of metalaxyl (44.5±21.5% of the initial mass spiked in the soils), S-metolachlor (8.1±3.1%) and Cu (3.1±0.3%). Soil compaction caused by the first rainfall reduced in the second rainfall the leaching of remaining metalaxyl, S-metolachlor, Cu and Zn by 2.4-, 2.9-, 30- and 50-fold, respectively. In contrast, soil characteristics and aging had less influence on pollutant mass export. The soil type significantly influenced the leaching of Zn, while short-term aging impacted Cu leaching. Our results suggest that rainfall characteristics predominantly control export patterns of metalaxyl and S-metolachlor, in particular when the aging period is short. We anticipate our study to be a starting point for more systematic evaluation of the dissolved pollutant ponding/leaching partitioning and the export of pollutant mixtures from different soil types in relation to rainfall patterns.

High frequency monitoring of pesticides in runoff water to improve understanding of their transport and environmental impacts.

Rainfall-induced peaks in pesticide concentrations can occur rapidly. Low frequency sampling may therefore largely underestimate maximum pesticide concentrations and fluxes. Detailed storm-based sampling of pesticide concentrations in runoff water to better predict pesticide sources, transport pathways and toxicity within the headwater catchments is lacking. High frequency monitoring (2min) of seven pesticides (Dimetomorph, Fluopicolide, Glyphosate, Iprovalicarb, Tebuconazole, Tetraconazole and Triadimenol) and one degradation product (AMPA) were assessed for 20 runoff events from 2009 to 2012 at the outlet of a vineyard catchment in the Layon catchment in France. The maximum pesticide concentrations were 387µgL-1. Samples from all of the runoff events exceeded the legal limit of 0.1µgL-1 for at least one pesticide (European directive 2013/39/EC). High resolution sampling used to detect the peak pesticide levels revealed that Toxic Units (TU) for algae, invertebrates and fish often exceeded the European Uniform principles (25%). The point and average (time or discharge-weighted) concentrations indicated up to a 30- or 4-fold underestimation of the TU obtained when measuring the maximum concentrations, respectively. This highlights the important role of sampling methods for assessing peak exposure. High resolution sampling combined with concentration-discharge hysteresis analyses revealed that clockwise responses were predominant (52%), indicating that Hortonian runoff is the prevailing surface runoff trigger mechanism in the study catchment. The hysteresis patterns for suspended solids and pesticides were highly dynamic and storm- and chemical-dependent. Intense rainfall events induced stronger C-Q hysteresis (magnitude). This study provides new insights into the complexity of pesticide dynamics in runoff water and highlights the ability of hysteresis analysis to improve understanding of pesticide supply and transport.

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.

Fungicides transport in runoff from vineyard plot and catchment: contribution of non-target areas.

Surface runoff and erosion during the course of rainfall events are major processes of pesticides transport from agricultural land to aquatic ecosystem. These processes are generally evaluated either at the plot or the catchment scale. Here, we compared at both scales the transport and partitioning in runoff water of two widely used fungicides, i.e., kresoxim-methyl (KM) and cyazofamid (CY). The objective was to evaluate the relationship between fungicides runoff from the plot and from the vineyard catchment. The results show that seasonal exports for KM and CY at the catchment were larger than those obtained at the plot. This underlines that non-target areas within the catchment largely contribute to the overall load of runoff-associated fungicides. Estimations show that 85 and 62 % of the loads observed for KM and CY at the catchment outlet cannot be explained by the vineyard plots. However, the partitioning of KM and CY between three fractions, i.e., the suspended solids (>0.7 µm) and two dissolved fractions (i.e., between 0.22 and 0.7 µm and <0.22 µm) in runoff water was similar at both scales. KM was predominantly detected below 0.22 µm, whereas CY was mainly detected in the fraction between 0.22 and 0.7 µm. Although KM and CY have similar physicochemical properties and are expected to behave similarly, our results show that their partitioning between two fractions of the dissolved phase differs largely. It is concluded that combined observations of pesticide runoff at both the catchment and the plot scales enable to evaluate the sources areas of pesticide off-site transport.