Compound-specific isotope analysis (CSIA) of micropollutants in the environment — current developments and future challenges

Over the last decade, the occurrence of micropollutants in the environment has become a worldwide issue of increasing concern. Compound-specific stable-isotope analysis (CSIA) of natural isotopic abundance may greatly enhance the evaluation of sources and transformation processes of micropollutants, such as pesticides, personal care products or pharmaceuticals. We summarize recent advances from laboratory studies, review current limitations and analytical challenges associated with low concentrations and high polarity of micropollutants, and delineate the potential of micropolluant CSIA for field applications. We highlight future challenges and prospects regarding source apportionment, identification of biotic and abiotic transformation reactions on a mechanistic level, as well as integrative evaluation of degradation hot spots on the catchment scale. Such advances may feed into a framework for risk assessment of micropollutants that includes CSIA

Toward Integrative Bacterial Monitoring of Metolachlor Toxicity in Groundwater

Common herbicides such as metolachlor (MET), and their transformation products, are frequently detected in groundwater worldwide. Little is known about the response of groundwater bacterial communities to herbicide exposure, and its potential use for ecotoxicological assessment. The response of bacterial communities exposed to different levels of MET from the Ariège alluvial aquifer (Southwest of France) was investigated in situ and in laboratory experiments. Variations in both chemistry and bacterial communities were observed in groundwater, but T-RFLP analysis did not allow to uncover a pesticide-specific effect on endogenous bacterial communities. To circumvent issues of hydrogeochemical and seasonal variations in situ, groundwater samples from two monitoring wells of the Ariège aquifer with contrasting records of pesticide contamination were exposed to different levels of MET in laboratory experiments. The standard Microtox® acute toxicity assay did not indicate toxic effects of MET, even at 5 mg L-1 (i.e., 1000-fold higher than in contaminated groundwater). Analysis of MET transformation products and compound-specific isotope analysis (CSIA) in laboratory experiments demonstrated MET biodegradation but did not correlate with MET exposure. High-throughput sequencing analysis (Illumina MiSeq) of bacterial communities based on amplicons of the 16S rRNA gene revealed that bacterial community differed mainly by groundwater origin rather than by its response to MET exposure. OTUs correlating with MET addition ranged between 0.4 to 3.6% of the total. Predictive analysis of bacterial functions impacted by pesticides using PICRUSt suggested only minor changes in bacterial functions with increasing MET exposure. Taken together, results highlight MET biodegradation in groundwater, and the potential use of bacterial communities as sensitive indicators of herbicide contamination in aquifers. Although detected effects of MET on groundwater bacterial communities were modest, this study illustrates the potential of integrating DNA- and isotopic analysis-based approaches to improve ecotoxicological assessment of pesticide-contaminated aquifers. GRAPHICAL ABSTRACTAn integrative approach was develop to investigate in situ and in laboratory experiments the response of bacterial communities exposed to different levels of MET from the Ariége alluvial aquifer (Southwest of France)

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

Atténuation et transport par ruissellement des pesticides dans les têtes de bassins versants agricoles (de la caractérisation sur le terrain à la modélisation)

Comprendre le transport des pesticides est crucial pour évaluer leur impact écologique. Les connaissances sur la variabilité spatiale des dépôts de pesticides, l'impact de l'érosion sur leur export et leur dégradation in situ restent très limitées à l'échelle des bassins versants. La caractérisation expérimentale et la modélisation ont donc été combinées à deux échelles, parcelle et bassin versant, dans deux contextes agricoles. Un formalisme a été développé pour prédire le transport des pesticides par ruissellement et a été intégré dans le modèle LISEM (LImbourg Soil Erosion Model). Les résultats montrent que les surfaces imperméables contribuent significativement à la masse exportée par ruissellement du vignoble. La partition des pesticides entre phase dissoute et particulaire diffère considérablement selon les molécules et le forçage hydrologique, et la présence de produits de dégradation et un enrichissement en R-métolachlore ont été observés ce qui souligne le potentiel des analyses énantiomériques pour évaluer la biodégradation des pesticides. Globalement, cette étude a démontré que la combinaison des échelles et des approches permet une meilleure compréhension du transport des pesticides.Understanding pesticide transport is crucial to evaluate their ecological impact on ecosystems. Current knowledge on the spatial variability of pesticide deposition, the impact of erosion on pesticides export and the in situ pesticide degradation is very limited at the catchment scale. In this thesis, characterisation and modeling at two scales, the plot and catchment, were combined in two agricultural contexts. A formalism was developed to predict pesticide transport in runoff and was integrated in LISEM (LImbourg Soil Erosion Model). The results show that impermeable roads contributed to more than 40% to the overall load of fungicides exported via runoff from the vineyard. Pesticide partitioning between suspended solids and runoff water differed largely according to the molecules and the hydrological dynamics. The occurrence of degradation products and the enrichment of one enantiomer were observed suggesting the potential of chiral analyses for assessing biodegradation of chiral pesticides at such scale. Overall, the investigation demonstrated that combining different approaches enable a better understanding of pesticide transport.STRASBOURG-Bib.electronique 063 (674829902) / SudocSudocFranceF

Transport et dégradation de pesticides en zones humides (une approche multi-échelles)

La compréhension des mécanismes de transport et de dégradation des pesticides émergents est primordiale pour prédire leur devenir dans l environnement. Les zones humides peuvent intercepter des eaux de ruissellement ou des souterraines contaminées par les pesticides et les traiter par le biais de processus de rétention et de dégradation, encore peu connus. Dans une approche multi-échelles, trois zones humides recevant des eaux polluées par les pesticides ont été utilisées comme des laboratoires naturels pour étudier le devenir de pesticides couramment utilisés. Cette thèse souligne l influence des conditions hydrologiques et redox sur la distribution des pesticides au sein des différents compartiments des zones humides ainsi que sur leur potentiel de dégradation. Alors que les études à grande échelle fournissent des informations intégratives sur la dissipation et la rétention des pesticides en lien avec le développement de la végétation, les études à petite échelle utilisant des techniques innovantes telles que les analyses isotopiques et énantiomériques permettent l exploration des processus moléculaires de dégradation des pesticides.A mechanistic understanding of transport and degradation processes of modern agricultural pesticides, including chiral pesticides, is critical for predicting their fate in the environment. In agricultural landscapes, wetlands can intercept pesticide-contaminated runoff or groundwater and improve water quality through various retention and degradation processes, which remain unknown. In a downscaling approach, three different wetlands receiving agricultural runoff were used as natural laboratories to investigate the fate of widely used pesticides. Overall, our results showed that dynamics of hydrological and redox conditions largely influenced pesticide sorption mechanisms and their distribution over time within wetland compartments, thereby controlling degradation processes. While large-scale studies provide integrative information on pesticide dissipation and distribution patterns with respect to wetland functioning, small-scale investigations using novel methods such as isotope and enantiomer analyses characterize underlying molecular processes governing pesticide degradation.STRASBOURG-Bib.electronique 063 (674829902) / SudocSudocFranceF

Measuring the effects of pesticides on bacterial communities in soil: A critical review

International audienceExtensive application of industrially-produced pesticides in agriculture has resulted in contamination of soil ecosystems. A variety of both cultivation-dependent and cultivation-independent methods can be applied to measure and interpret the effects of pesticide exposure. We review here the expanding panel of these methods in the specific context of responses of the soil bacterial microflora to pesticide exposure, and of ongoing advances in microbial molecular ecology, including metagenomics and new approaches for DNA sequencing. Several issues still need to be addressed in order to routinely evaluate the effect of pesticides on bacterial communities in soil in the future, and to make way for a widely accepted framework for risk assessment in agro-ecosystems that include bacterial indicators. (C) 2011 Elsevier Masson SAS. All rights reserved

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

International audienc

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

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

International audienceTerbutryn 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