The Role of Ponds in Pesticide Dissipation at the Agricultural Catchment Scale: A Critical Review

Ponds in agricultural areas are ubiquitous water retention systems acting as reactive biogeochemical hotspots controlling pesticide dissipation and transfer at the catchment scale. Several issues need to be addressed in order to understand, follow-up and predict the role of ponds in limiting pesticide transfer at the catchment scale. In this review, we present a critical overview of functional processes underpinning pesticide dissipation in ponds. We highlight the need to distinguish degradative and non-degradative processes and to understand the role of the sediment-water interface in pesticide dissipation. Yet it is not well-established how pesticide dissipation in ponds governs the pesticide transfer at the catchment scale under varying hydro-climatic conditions and agricultural operation practices. To illustrate the multi-scale and dynamic aspects of this issue, we sketch a modelling framework integrating the role of ponds at the catchment scale. Such an integrated framework can improve the spatial prediction of pesticide transfer and risk assessment across the catchment-ponds-river continuum to facilitate management rules and operations

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

International audiencePesticide degradation in wetland systems intercepting agricultural runoff is often overlooked and mixed with other dissipation processes when estimated based on 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 13 C>3 ‰) in its carbon isotopic composition in the wetland water compared to the runoff and commercial formulation, indicating 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 degradatio

Performance of the Wet Oxidation Unit of the HPLC Isotope Ratio Mass Spectrometry System for Halogenated Compounds

The performance of liquid chromatography–isotope ratio mass spectrometry (LC-IRMS) for polar halogenated compounds was evaluated. Oxidation capacity of the system was tested with halogenated acetic acids and halogenated aromatic compounds. Acetic acid (AA) was selected as a reference compound for complete oxidation and compared on the molar basis to the oxidation of other analytes. The isotope values were proofed with calibrated δ¹³C values obtained with an elemental analyzer (EA). Correct isotope values were obtained for mono- and dichlorinated, fluorinated, and tribrominated acetic acids and also for aniline, phenol, benzene, bromobenzene, chlorobenzene, 1,2-dichlorobenzene, 2,4,6-trichlorophenol, pentafluorophenol, and nitrobenzene. Incomplete oxidation of trichloroacetic acid (TCA) and trifluoroacetic acid (TFA) resulted in lower recovery compared to AA (37% and 24%, respectively) and in isotopic shift compared to values obtained with EA (TCA Δδ¹³C_EA/LC‑IRMS = 8.8‰, TFA Δδ¹³C_EA/LC‑IRMS = 6.0‰). Improvement of oxidation by longer reaction time in the reactor and increase in the concentration of sulfate radicals did not lead to complete combustion of TCA and TFA needed for δ¹³C analysis. To the best of our knowledge, this is the first time such highly chlorinated compounds were studied with the LC-IRMS system. This work provides information for method development of LC-IRMS methods for halogenated contaminants that are known as potential threats to public health and the environment

Simple extraction methods for pesticide compound-specific isotope analysis from environmental samples

International audienceCompound-specific isotope analysis (CSIA) is a powerful approach to track the fate of organic pollutants in the environment. However, the application of CSIA to micropollutants, such as pesticides, remains limited because appropriate extraction methods are currently lacking. Such methods should address a wide range of pesticides and environmental matrices and allow recovering sufficient mass for reliable CSIA without inducing stable isotope fractionation. Here, we present simple extraction methods for carbon (13 C/ 12 C) and nitrogen (15 N/ 14 N) CSIA for different environmental matrices and six commonly used herbicides, i.e., atrazine, terbutryn, acetochlor, alachlor, butachlor, and S-metolachlor, and three fungicides, i.e., dimethomorph, tebuconazole, and metalaxyl. We examined the potential of several extraction methods for four types of soils or sediments, three types of environmental waters and aerial and root plant samples for multielement (ME)-CSIA

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

International audiencePesticides 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 pes-ticide degradation in artificial ponds and agricultural streams. The application of pesticide CSIA to surface waters is cur-rently 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 sce-narios. 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)orthe flow speeds(6or14cm.s−1). However, simulated rainfall events of pesticide runoff affected the δ13C of pesticidesinPOCIS. 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 com-mercial 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