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.

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.

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.

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.

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.