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During wastewater treatment, incomplete elimination of micropollutants occurs. Recently, the potential impacts of the release of some micropollutants at the scale of France have been studied. These impact calculations were incomplete due to a lack of characterization factors (CFs). In the present study, we used already developed machine learning models to complement the missing CFs. The conclusions were not modified for the impact on aquatic environment, but were mitigated for the impact on human health: the higher toxicological potential impact could be driven by a high-emitted mass, and a high number of compounds could take a significant part of the overall impact.

One current challenge in sustainable agriculture is to redesign cropping systems to reduce the use and impacts of pesticides, and by doing so protect the environment, in particular groundwater, and human health. As a large range of systems could be explored and a wide number of pesticides used, field experiments cannot be carried out to study the sustainability of each of them. Thus, the objectives of this work were (1) to measure water flows and pesticide leaching in six contrasted low input cropping systems based on sunflower-wheat rotation, oilseed rape-wheat-barley rotation, and maize monoculture, experimented for three years in three different soil and climatic conditions, and (2) to assess and to compare the ability of three pesticide fate models (MACRO, PEARL, PRZM) to simulate the observed water flows and pesticide concentrations. The systems were designed using various crop rotations, including cover crops and intercrops. The models were parameterized with generic parameter estimation routines as done for regulatory risk assessment, and a method was developed to parameterize intercrops, not represented in the models: the use of average crop factors, maximum LAI, crop height and rooting depth of the crops constituting the intercrop allowed acceptable simulations of cumulative water flows, but not their dynamic. Twelve pesticides of 70 applied were quantified in lysimeter samples (e.g. bentazone, glyphosate, S-metolachlor), and their concentrations exceeded 0.1 μg L -1 in several occasions. The performance of the models to reproduce pesticide concentrations was generally poor illustrating the great challenge and the progress needed to simulate accurately pesticide transfers into the soil. The best fits to measured data were attained using "worst-case" pesticide sorption and degradation parameters. Overall, MACRO performed better than PEARL and PRZM. The method developed to parameterize intercrops could be used for risk assessment of groundwater contamination by pesticides in low input cropping systems, but the use of the three models without any calibration is likely to underestimate pesticide leaching in several situations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

The intensification of agriculture has promoted the simplification and specialization of agroecosystems, resulting in negative impacts such as decreasing landscape heterogeneity and increasing use of plant protection products (PPP), with the acceleration of PPP transfers to environmental compartments and loss in biodiversity. In this context, the present work reviews the various levers for action promoting the prevention and management of these transfers in the environment and the available modelling tools. Two main categories of levers were identified: (1) better control of the application, including the reduction of doses and of PPP dispersion during application thanks to appropriate equipment and settings, PPP formulations and consideration of meteorological conditions; (2) reduction of post-application transfers at plot scales (soil cover, low tillage, organic matter management, remediation etc. and at landscape scales using either dry (grassed strips, forest, hedgerows and ditches) or wet (ponds, mangroves and stormwater basins) buffer zones. The management of PPP residues leftover in the spray tanks (biobeds) also represents a lever for limiting point-source PPP pollution. Numerous models have been developed to simulate the transfers of PPPs at plot scales. They are scarce for landscape scales. A few are used for regulatory risk assessment. These models could still be improved, for example, if current agricultural practices (e.g. agro-ecological practices and biopesticides), and their effect on PPP transfers were better described. If operated alone, none of the levers guarantee a zero risk of PPP transfer. However, if levers are applied in a combined manner, PPP transfers could be more easily limited (agricultural practices, landscape organization etc.)., Competing Interests: Declarations. Ethics approval and consent to participate: Not applicable Consent to publish: Not applicable. Competing interests: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Plant protection products (PPP) are extensively used to protect plants against harmful organisms, but they also have unintended effects on non-target organisms, especially terrestrial invertebrates. The impact of PPP on ecosystem functions provided by these non-target invertebrates remains, however, unclear. The objectives of this article were to review PPP impacts on the ecosystem functions provided by pollinators, predators and parasitoids, and soil organisms, and to identify the factors that aggravate or mitigate PPP effects. The literature highlights that PPP alter several ecosystem functions: provision and maintenance of biodiversity, pollination, biotic interactions and habitat completeness in terrestrial ecosystems, and organic matter and soil structure dynamics. However, there are still a few studies dealing with ecosystem functions, with sometimes contradictory results, and consequences on agricultural provisioning services remain unclear. The model organisms used to assess PPP ecotoxicological effects are still limited, and should be expanded to better cover the wide functional diversity of terrestrial invertebrates. Data are lacking on PPP sublethal, transgenerational, and "cocktail" effects, and on their multitrophic consequences. In empirical assessments, studies on PPP unintended effects should consider agricultural-pedoclimatic contexts because they influence the responses of non-target organisms and associated ecosystem functions to PPP. Modeling might be a promising way to account for the complex interactions among PPP mixtures, biodiversity, and ecosystem functioning., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The placing of plant protection products (PPPs) on the market in the European Union is governed by numerous regulations. These regulations are among the most stringent in the world, however they have been the subject of criticisms especially because of the decline in biodiversity. The objectives of this work were to review (1) the functioning and actors involved in the PPP framework processes, (2) the construction of the environmental risk assessment focused on biodiversity, and (3) the suggested ways to respond to the identified limits. Both literature from social sciences and ecotoxicology were examined. Despite the protective nature of the European regulation on PPPs, the very imperfect consideration of biodiversity in the evaluation process was underlined. The main limits are the multiplicity of applicable rules, the routinization of the evaluation procedures, the lack of consideration of social data, and the lack of independence of the evaluation. Strengths of the regulation are the decision to integrate a systemic approach in the evaluation of PPPs, the development of modeling tools, and the phytopharmacovigilance systems. The avenues for improvement concern the realism of the risk assessment (species used, cocktail effects…), a greater transparency and independence in the conduct of evaluations, and the opening of the evaluation and decision-making processes to actors such as beekeepers or NGOs. Truly interdisciplinary reflections crossing the functioning of the living world, its alteration by PPPs, and how these elements question the users of PPPs would allow to specify social actions, public policies, and their regulation to better protect biodiversity., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Biocontrol solutions (macroorganisms, microorganisms, natural substances, semiochemicals) are presented as potential alternatives to conventional plant protection products (PPPs) because they are supposed to have lower impacts on ecosystems and human health. However, to ensure the sustainability of biocontrol solutions, it is necessary to document the unintended effects of their use. Thus, the objectives of this work were to review (1) the available biocontrol solutions and their regulation, (2) the contamination of the environment (soil, water, air) by biocontrol solutions, (3) the fate of biocontrol solutions in the environment, (4) their ecotoxicological impacts on biodiversity, and (5) the impacts of biocontrol solutions compared to those of conventional PPPs. Very few studies concern the presence of biocontrol solutions in the environment, their fate, and their impacts on biodiversity. The most important number of results were found for the organisms that have been used the longest, and most often from the angle of their interactions with other biocontrol agents. However, the use of living organisms (microorganisms and macroorganisms) in biocontrol brings a specific dimension compared to conventional PPPs because they can survive, multiply, move, and colonize other environments. The questioning of regulation stems from this specific dimension of the use of living organisms. Concerning natural substances, the few existing results indicate that while most of them have low ecotoxicity, others have a toxicity equivalent to or greater than that of the conventional PPPs. There are almost no result regarding semiochemicals. Knowledge of the unintended effects of biocontrol solutions has proved to be very incomplete. Research remains necessary to ensure their sustainability., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Copper-based plant protection products (PPPs) are widely used in both conventional and organic farming, and to a lesser extent for non-agricultural maintenance of gardens, greenspaces, and infrastructures. The use of copper PPPs adds to environmental contamination by this trace element. This paper aims to review the contribution of these PPPs to the contamination of soils and waters by copper in the context of France (which can be extrapolated to most of the European countries), and the resulting impacts on terrestrial and aquatic biodiversity, as well as on ecosystem functions. It was produced in the framework of a collective scientific assessment on the impacts of PPPs on biodiversity and ecosystem services in France. Current science shows that copper, which persists in soils, can partially transfer to adjacent aquatic environments (surface water and sediment) and ultimately to the marine environment. This widespread contamination impacts biodiversity and ecosystem functions, chiefly through its effects on phototrophic and heterotrophic microbial communities, and terrestrial and aquatic invertebrates. Its effects on other biological groups and biotic interactions remain relatively under-documented., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Preserving biodiversity against the adverse effects of plant protection products (PPPs) is a major environmental and societal issue. However, despite intensive investigation into the ecotoxicological effects of PPPs, the knowledge produced remains fragmented given the sheer diversity of PPPs. This is due, at least in part, to a strong streetlight effect in the field of ecotoxicology. Indeed, while some PPPs have been investigated in numerous ecotoxicological studies, there are many for which the scientific literature still has little or no information on their ecotoxicological risks and effects. The PPPs under the streetlight include a large variety of legacy substances and a more limited number of more recent or currently-in-use substances, such as the herbicide glyphosate and the neonicotinoid insecticides. Furthermore, many of the most recent PPPs (including those used in biocontrol) and PPP transformation products (TPs) resulting from abiotic and/or biotic degradation are rarely addressed in the international literature in the field of ecotoxicology. Here, based on a recent collective scientific assessment of the effects of PPPs on biodiversity and ecosystem services in the French and European contexts, this article sets out to illustrate the limitations and biases caused by the streetlight effect and numbers of gray areas, and issue recommendations on how to overcome them., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Neonicotinoids are the most widely used class of insecticides in the world, but they have raised numerous concerns regarding their effects on biodiversity. Thus, the objective of this work was to do a critical review of the contamination of the environment (soil, water, air, biota) by neonicotinoids (acetamiprid, clothianidin, imidacloprid, thiacloprid, thiamethoxam) and of their impacts on terrestrial and aquatic biodiversity. Neonicotinoids are very frequently detected in soils and in freshwater, and they are also found in the air. They have only been recently monitored in coastal and marine environments, but some studies already reported the presence of imidacloprid and thiamethoxam in transitional or semi-enclosed ecosystems (lagoons, bays, and estuaries). The contamination of the environment leads to the exposure and to the contamination of non-target organisms and to negative effects on biodiversity. Direct impacts of neonicotinoids are mainly reported on terrestrial invertebrates (e.g., pollinators, natural enemies, earthworms) and vertebrates (e.g., birds) and on aquatic invertebrates (e.g., arthropods). Impacts on aquatic vertebrate populations and communities, as well as on microorganisms, are less documented. In addition to their toxicity to directly exposed organisms, neonicotinoid induce indirect effects via trophic cascades as demonstrated in several species (terrestrial and aquatic invertebrates). However, more data are needed to reach firmer conclusions and to get a clearer picture of such indirect effects. Finally, we identified specific knowledge gaps that need to be filled to better understand the effects of neonicotinoids on terrestrial, freshwater, and marine organisms, as well as on ecosystem services associated with these biotas., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Preservation of biodiversity and ecosystem services is critical for sustainable development and human well-being. However, an unprecedented erosion of biodiversity is observed and the use of plant protection products (PPP) has been identified as one of its main causes. In this context, at the request of the French Ministries responsible for the Environment, for Agriculture and for Research, a panel of 46 scientific experts ran a nearly 2-year-long (2020-2022) collective scientific assessment (CSA) of international scientific knowledge relating to the impacts of PPP on biodiversity and ecosystem services. The scope of this CSA covered the terrestrial, atmospheric, freshwater, and marine environments (with the exception of groundwater) in their continuity from the site of PPP application to the ocean, in France and French overseas territories, based on international knowledge produced on or transposable to this type of context (climate, PPP used, biodiversity present, etc.). Here, we provide a brief summary of the CSA's main conclusions, which were drawn from about 4500 international publications. Our analysis finds that PPP contaminate all environmental matrices, including biota, and cause direct and indirect ecotoxicological effects that unequivocally contribute to the decline of certain biological groups and alter certain ecosystem functions and services. Levers for action to limit PPP-driven pollution and effects on environmental compartments include local measures from plot to landscape scales and regulatory improvements. However, there are still significant gaps in knowledge regarding environmental contamination by PPPs and its effect on biodiversity and ecosystem functions and services. Perspectives and research needs are proposed to address these gaps., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Before their placing on the market, the safety of plant protection products (PPP) towards both human and animal health, and the environment has to be assessed using experimental and modelling approaches. Models are crucial tools for PPP risk assessment and some even help to avoid animal testing. This review investigated the use of modelling approaches in the ecotoxicology section of PPP active substance assessment reports prepared by the authorities and opened to consultation from 2011 to 2021 in the European Union. Seven categories of models (Structure-Activity, ToxicoKinetic, ToxicoKinetic-ToxicoDynamic, Species Sensitivity Distribution, population, community, and mixture) were searched for into the reports of 317 active substances. At least one model category was found for 44 % of the investigated active substances. The most detected models were Species Sensitivity Distribution, Structure-Activity and ToxicoKinetic for 27, 21 and 15 % of the active substances, respectively. The use of modelling was of particular importance for conventional active substances such as sulfonylurea or carbamates contrary to microorganisms and plant derived substances. This review also highlighted a strong imbalance in model usage among the biological groups considered in the European Regulation (EC) No 1107/2009. For example, models were more often used for aquatic than for terrestrial organisms (e.g., birds, mammals). Finally, a gap between the set of models used in reports and those existing in the literature was observed highlighting the need for the implementation of more sophisticated models into PPP regulation., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Marie-France Corio-Costet reports a relationship with National Agency for Food Environmental and Occupational Health and Safety that includes: consulting or advisory, funding grants, and travel reimbursement. Philippe Berny reports a relationship with National Agency for Food Environmental and Occupational Health and Safety that includes: consulting or advisory and travel reimbursement. Philippe Berny reports a relationship with European Food Safety Authority that includes: consulting or advisory and travel reimbursement., (Copyright © 2022 Elsevier B.V. All rights reserved.)

A wide diversity of plant protection products (PPP) is used for crop protection leading to the contamination of soil, water, and air, which can have ecotoxicological impacts on living organisms. It is inconceivable to study the effects of each compound on each species from each compartment, experimental studies being time consuming and cost prohibitive, and animal testing having to be avoided. Therefore, numerous models are developed to assess PPP ecotoxicological effects. Our objective was to provide an overview of the modeling approaches enabling the assessment of PPP effects (including biopesticides) on the biota. Six categories of models were inventoried: (Q)SAR, DR and TKTD, population, multi-species, landscape, and mixture models. They were developed for various species (terrestrial and aquatic vertebrates and invertebrates, primary producers, micro-organisms) belonging to diverse environmental compartments, to address different goals (e.g., species sensitivity or PPP bioaccumulation assessment, ecosystem services protection). Among them, mechanistic models are increasingly recognized by EFSA for PPP regulatory risk assessment but, to date, remain not considered in notified guidance documents. The strengths and limits of the reviewed models are discussed together with improvement avenues (multigenerational effects, multiple biotic and abiotic stressors). This review also underlines a lack of model testing by means of field data and of sensitivity and uncertainty analyses. Accurate and robust modeling of PPP effects and other stressors on living organisms, from their application in the field to their functional consequences on the ecosystems at different scales of time and space, would help going toward a more sustainable management of the environment. Graphical Abstract Combination of the keyword lists composing the first bibliographic query. Columns were joined together with the logical operator AND. All keyword lists are available in Supplementary Information at https://doi.org/10.5281/zenodo.5775038 (Larras et al. 2021)., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Following treatment, amounts of pesticides can reach the atmosphere because of spray drift, volatilization from soil or plants, and/or wind erosion. Monitoring and risk assessment of air contamination by pesticides is a recent issue and more insights on pesticide transfer to atmosphere are needed. Thus, the objective of this work was to better understand and assess pesticides emission potential to air through volatilization. The TyPol tool was used to explore the relationships between the global, soil and plant volatilization potentials of 178 pesticides, and their molecular properties. The outputs of TyPol were then compared to atmospheric pesticide concentrations monitored in various French regions. TyPol was able to discriminate pesticides that were observed in air from those that were not. Clustering considering parameters driving the emission potential from soil (sorption characteristics) or plant (lipophilic properties), in addition to vapor pressure, allowed better discrimination of the pesticides than clustering considering all parameters for the global emission potential. Pesticides with high volatilization potential have high total energy, and low molecular weight, molecular connectivity indices and polarizability. TyPol helped better understand the volatilization potential of pesticides. It can be used as a first step to assess the risk of air contamination by pesticides., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Several sustainable development goals cannot be achieved without implementing a new generation of environmental measures to better preserve or restore biodiversity and ecosystem services. However, understanding and addressing biodiversity loss and ecosystem degradation is a challenging problem that is not solvable without integrating the best and latest science. It is crucial to enhance the legibility of this knowledge for decision-makers and policymakers following good-practice standards of scientific assessment. This is the main objective of collective scientific assessments (CSAs), as carried out by the French National Research Institute for Agriculture, Food and the Environment (INRAE) since the early 2000s following a documented procedure to inform public policy and foster public debate on complex interdisciplinary issues. This article describes the main steps of the CSA procedure designed by INRAE's Directorate for Collective Scientific Assessment, Foresight and Advanced Studies, from formulation of the initial question asked by public or para-public bodies (typically ministry divisions or environmental agencies) to wider dissemination of the results and conclusions. This process description is then illustrated through the example of a CSA recently commissioned by three French Ministries (for Ecology, for Research, and for Agriculture) regarding (i) contamination of terrestrial, freshwater, and marine ecosystems by plant protection products (PPPs); (ii) the resulting effects on biodiversity and ecosystem services; and (iii) possible prevention and mitigation strategies. The capacity of this kind of CSA to inform public debate and policymaking is then exemplified through a description of the main outcomes generated by the latest CSA dealing with the adverse effects of PPPs. We also provide a short overview of some key expectations from the current CSA, with a focus on the recent development of the ecosystem service approach in ecological risk assessments of PPPs in the European Union. This illustration demonstrates that CSAs, which are applicable to a wide variety of complex interdisciplinary questions that are not limited to environmental issues, are a relevant tool to inform public debate and policymaking., (© 2021. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Despite the richness of data collected on pesticide concentrations in ambient air in France, knowledge on this topic remains partial and heterogeneous in the absence of specific regulations. The population exposure remains thus difficult to estimate; therefore it was necessary to define modalities for implementing national monitoring of pesticides in ambient air in metropolitan France and in the overseas territories. The objective of this work was to identify which active substances (a.s.) have to be monitored in priority. As part of a collective expertise, a group of multidisciplinary experts has developed a method to rank active substances authorised as plant protection products, biocides and antiparasitic agents, which were available on the French market in 2015. A 3-steps approach has been developed. The first step consisted of a theoretical approach based on a hierarchy of substances according to four criteria: (a) national uses, (b) emission potential to the air, (c) persistence in the air, and (d) chronic toxicity. The three first criteria give information on their potential to be present in the atmosphere, and the fourth criterion allows to consider their potential of hazard. The second step was an observational approach based on existing database on pesticide air measurements in France. In the third step, both approaches were combined using decision trees to select priority pesticides. Among the 1316 a.s. first identified from the EU Pesticides database, 90 were selected, among which 43 required metrological and/or analytical development. The experts recommended confirming the relevance of performing a longer term monitoring of these a. s. after a one-year exploratory campaign. The proposed method is reproduceable, transparent, easy to update (e.g. in the light of a change in product authorization), and can be adapted to other agricultural and geographical conditions, and objectives (e.g. monitoring of the ecotoxicological effects of pesticides)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020. Published by Elsevier B.V.)

The dissipation and persistence of two cereals herbicides, chlorotoluron and flufenacet, were studied in a field experiment including three replicated plots of unamended soil (S), soil amended with spent mushroom substrate (S + SMS), and soil amended with green compost (S + GC), during the winter wheat cultivation campaign. The SMS and GC organic residues were applied to the soil at rates of 140 or 85 t residue ha -1 , and herbicides were sprayed as Erturon® and Herold® formulations for chlorotoluron and flufenacet, respectively. Concentrations of both herbicides and of their metabolites were regularly measured in the three soil treatments (0-10 cm) from 0 to 339 days. The dissipation kinetics fitted well the single first order (SFO) model, except that of chlorotoluron that fitted the first order multi-compartment (FOMC) model better in the unamended soil. The dissipation rates of herbicides were lower in amended than in unamended soils. The results also showed that the DT 50 of chlorotoluron (66.2-88.0 days) and flufenacet (117-145 days) under field conditions were higher than those previously obtained at laboratory scale highlighting the importance of the changing environmental conditions on the dissipation process. Similarly, the formation of chlorotoluron and flufenacet metabolites under field conditions was different from that previously observed in the laboratory. The performance of the MACRO pesticide fate model, parameterized with laboratory data, was then tested against field data. There was a very good agreement between measured and simulated chlorotoluron residue levels in the three soil treatments, while the ability of the model to reproduce the dissipation of flufenacet was good in the unamended soil and very good in S + SMS and S + GC soils. MACRO might be used to estimate the remaining amounts of herbicides in amended soils from degradation data previously obtained at laboratory scale. This would help to manage herbicide doses in different environmental conditions to preserve the sustainability of agricultural systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Addition of organic residues to soil is a current farming practice but it is not considered in the modelling studies for pesticide risk assessment at regulatory level despite its potential impact on the pesticide dynamics in soil. Thus, the objective of this work was to examine and to compare the ability of PRZM and MACRO pesticide fate models to simulate soil water content, and bromide (Br - , tracer), chlorotoluron and flufenacet concentrations in the soil profiles (0-100 cm) of one agricultural soil, unamended (control soil, S), amended with spent mushroom substrate (S + SMS) or amended with green compost (S + GC). Based on a two-year field-scale dataset, the models were first calibrated against measurements of water and solutes contents in the soil profiles (first year) and then tested without any further model calibration by comparison with the field observations of the second year. In general, the performance of MACRO to simulate the whole dataset in the three soil treatments was higher than that of PRZM. MACRO simulated satisfactorily the water dynamics along the soil profiles whereas it was poorly described by the capacity model PRZM. Both models predicted very well the Br - mobility in control and amended soils after dispersion parameters were fitted to observations. No calibration was necessary to reproduce correctly herbicides vertical distribution in the control soil profile. In the amended soils, MACRO simulations were highly correlated to the observed vertical distribution of flufenacet and chlorotoluron, but calibration of the K d of chlorotoluron was needed. On the contrary, modelling with PRZM required calibration of K d and DT 50 of both herbicides to obtain an acceptable agreement between observations and predictions in the amended soils. K d and DT 50 calibration was based on the initial dissolved organic carbon contents (DOC) of amended soils. It allowed to take into account the processes that decrease the herbicides sorption on the soil and enhance their bioavailability, but that are not described in PRZM and MACRO (such as the formation of herbicide-DOC mobile complexes). This work showed that models such as PRZM and MACRO are able to simulate the fate of pesticides in amended soils. However, before using these models as predictive tools in large amended soil conditions, and especially in the regulatory context, further modelling studies should focus on other pedoclimatic-pesticides-organic residues combinations, and on longer periods., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Conservation tillage practices mainly based on cover crops and no-tillage with accumulation of crop residues at the soil surface (mulch) modify the environmental fate of pesticides. However, only few pesticide fate models are able to consider mulch of crop residues as well as the effect of intermediate cover crops. Thus, the objective was to develop an approach to model the effects of crop residues left at the soil surface and cover crops on the fate of pesticides. This approach consisted in (1) considering the crop residues as a soil layer with specific physical, hydrodynamic and pesticide-reactivity properties close to that of a high organic content soil layer, and (2) introducing a correction factor of the potential evapotranspiration, estimated through a calibration step, to take into account the reduction of soil evaporation by the presence of a mulch. This approach was developed using MACRO as support pesticide model. To assess the model performances, we used the data from a field experiment designed in an irrigated maize monoculture under conservation tillage. Soil water content, water percolates, soil temperature and S-metolachlor herbicide concentrations in the leachate at 1m depth were measured during two years. The approach chosen to simulate the mulch effects allowed MACRO to make acceptable predictions of the observed water percolation, soil temperature and to a less extent herbicide leaching. However, it showed a poor performance to simulate the soil water content. Results are discussed in terms of further modelling options to better assess the environmental risks of pesticides under conservation tillage. This approach remains to be tested against various soils, crops, pesticides and types of mulch., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Understanding the fate and ecotoxicological effects of pesticides largely depends on their molecular properties. We recently developed "TyPol" (Typology of Pollutants), a classification method of organic compounds based on statistical analyses. It combines several environmental (sorption coefficient, degradation half-life) and one ecotoxicological (bioconcentration factor) parameters, to structural molecular descriptors (number of atoms in the molecule, molecular surface, dipole moment, energy of orbitals, etc.). The present study attempts to extend TyPol to the ecotoxicological effects of pesticides on non-target organisms, based on data analysis from available literature and databases. It revealed that relevant ecotoxicological endpoints for terrestrial organisms (e.g., soil microorganisms, invertebrates) that support a range of ecosystemic services are lacking as compared to aquatic organisms. The availability of ecotoxicological parameters was also lower for chronic than for acute ecotoxicity endpoints. Consequently, seven parameters were included for acute (EC50, LC50) and chronic (NOEC) ecotoxicological effects for one terrestrial (Eisenia sp.) and three aquatic (Daphnia sp., algae, Lemna sp.) organisms. In this new configuration, we used TyPol to classify 50 pesticides into different clusters that gather molecules with similar environmental behaviors and ecotoxicological effects. The classification results evidenced relationships between molecular descriptors, environmental parameters, and the added ecotoxicological endpoints. This proof-of-concept study also showed that TyPol in silico classification can successfully address new scientific questions and be expanded with other parameters of interest.

Background: Reducing the risks and impacts of pesticide use on human health and on the environment is one of the objectives of the European Commission Directive 2009/128/EC in the quest for a sustainable use of pesticides. This Directive, developed through European national plans such as Ecophyto plan in France, promotes the introduction of innovative cropping systems relying, for example, on integrated pest management. Risk assessment for human health of the overall pesticide use in these innovative systems is required before the introduction of those systems to avoid that an innovation becomes a new problem., Objectives: The objectives of this work were to assess and to compare (1) the human exposure to pesticides used in conventional and innovative cropping systems designed to reduce pesticide needs, and (2) the corresponding risks for human health., Methods: Humans (operator and residents) exposure to pesticides and risks for human health were assessed for each pesticide with the BROWSE model. Then, a method was proposed to represent the overall risk due to all pesticides used in one system. This study considers 3 conventional and 9 associated innovative cropping systems, and 116 plant protection products containing 89 different active substances (i.e. pesticides)., Results: The modelling results obtained with BROWSE showed that innovative cropping systems such as low input or no herbicide systems would reduce the risk for human health in comparison to the corresponding conventional cropping systems. On the contrary, BROWSE showed that conservation tillage system would lead to unacceptable risks in the conditions of our study, because of a high number of pesticide applications, and especially of some herbicides. For residents, the dermal absorption was the main exposure route while ingestion was found to be negligible. For operators, inhalation was also a predominant route of exposure. In general, human exposure to pesticides and human health risks were found to be correlated to the treatment frequency index TFI (number of registered doses of pesticides used per hectare for one copping season), confirming the relationship between the reduction of pesticide use and the reduction of risks., Conclusions: Assessment with the BROWSE model helped to identify cropping systems with decreased risks from pesticides for human health and to propose some improvements to the cropping systems by identifying the pesticides that led to unacceptable risks., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The current challenge in sustainable agriculture is to introduce new cropping systems to reduce pesticides use in order to reduce ground and surface water contamination. However, it is difficult to carry out in situ experiments to assess the environmental impacts of pesticide use for all possible combinations of climate, crop, and soils; therefore, in silico tools are necessary. The objective of this work was to assess pesticides leaching in cropping systems coupling the performances of a crop model (STICS) and of a pesticide fate model (MACRO). STICS-MACRO has the advantage of being able to simulate pesticides fate in complex cropping systems and to consider some agricultural practices such as fertilization, mulch, or crop residues management, which cannot be accounted for with MACRO. The performance of STICS-MACRO was tested, without calibration, from measurements done in two French experimental sites with contrasted soil and climate properties. The prediction of water percolation and pesticides concentrations with STICS-MACRO was satisfactory, but it varied with the pedoclimatic context. The performance of STICS-MACRO was shown to be similar or better than that of MACRO. The improvement of the simulation of crop growth allowed better estimate of crop transpiration therefore of water balance. It also allowed better estimate of pesticide interception by the crop which was found to be crucial for the prediction of pesticides concentrations in water. STICS-MACRO is a new promising tool to improve the assessment of the environmental risks of pesticides used in cropping systems.

STICS-MACRO is a process-based model simulating the fate of pesticides in the soil-plant system as a function of agricultural practices and pedoclimatic conditions. The objective of this work was to evaluate the influence of crop management practices on water and pesticide flows in contrasted environmental conditions. We used the Morris screening sensitivity analysis method to identify the most influential cropping practices. Crop residues management and tillage practices were shown to have strong effects on water percolation and pesticide leaching. In particular, the amount of organic residues added to soil was found to be the most influential input. The presence of a mulch could increase soil water content so water percolation and pesticide leaching. Conventional tillage was also found to decrease pesticide leaching, compared to no-till, which is consistent with many field observations. The effects of the soil, crop and climate conditions tested in this work were less important than those of cropping practices. STICS-MACRO allows an ex ante evaluation of cropping systems and agricultural practices, and of the related pesticides environmental impacts., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Chlordecone (C 10 Cl 10 O; CAS number 143-50-0) has been used extensively as an organochlorine insecticide but is nowadays banned and listed on annex A in The Stockholm Convention on Persistent Organic Pollutants (POPs). Although experimental evidences of biodegradation of this compound are scarce, several dechlorination products have been proposed by Dolfing et al. (2012) using Gibbs free energy calculations to explore different potential transformation routes. We here present the results of an in silico classification (TyPol - Typology of Pollutants) of chlordecone transformation products (TPs) based on statistical analyses combining several environmental endpoints and structural molecular descriptors. Starting from the list of putative chlordecone TPs and considering available data on degradation routes of other organochlorine compounds, we used different clustering strategies to explore the potential environmental behaviour of putative chlordecone TPs from the knowledge on their molecular descriptors. The method offers the possibility to focus on TPs present in different classes and to infer their environmental fate. Thus, we have deduced some hypothetical trends for the environmental behaviour of TPs of chlordecone assuming that TPs, which were clustered away from chlordecone, would have different environmental fate and ecotoxicological impact compared to chlordecone. Our findings suggest that mono- and di-hydrochlordecone, which are TPs of chlordecone often found in contaminated soils, may have similar environmental behaviour in terms of persistence., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A significant fraction of pesticides sprayed on crops may be returned to soils via plant residues, but its fate has been little documented. The objective of this work was to study the fate of glyphosate associated to plants residues. Oilseed rape was used as model plant using two lines: a glyphosate-tolerant (GT) line and a non-GT one, considered as a crucifer weed. The effects of different fragmentation degrees and placements in soil of plant residues were tested. A control was set up by spraying glyphosate directly on the soil. The mineralization of glyphosate in soil was slower when incorporated into plant residues, and the amounts of extractable and non-extractable glyphosate residues increased. Glyphosate availability for mineralization increased when the size of plant residues decreased, and as the distribution of plant residues in soil was more homogeneous. After 80 days of soil incubation, extractable (14)C-residues mostly involved one metabolite of glyphosate (AMPA) but up to 2.6% of initial (14)C was still extracted from undecayed leaves as glyphosate. Thus, the trapping of herbicides in plant materials provided a protection against degradation, and crops residues returns may increase the persistence of glyphosate in soils. This pattern appeared more pronounced for GT crops, which accumulated more non-degraded glyphosate in their tissues., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Pesticides generate transformation products (TPs) when they are released into the environment. These TPs may be of ecotoxicological importance. Past studies have demonstrated how difficult it is to predict the occurrence of pesticide TPs and their environmental risk. The monitoring approaches mostly used in current regulatory frameworks target only known ecotoxicologically relevant TPs. Here, we present a novel combined approach which identifies and categorizes known and unknown pesticide TPs in soil by combining suspect screening time-of-flight mass spectrometry with in silico molecular typology. We used an empirical and theoretical pesticide TP library for compound identification by both non-target and target time-of-flight (tandem) mass spectrometry, followed by structural proposition through a molecular structure correlation program. In silico molecular typology was then used to group TPs according to common molecular descriptors and to indirectly elucidate their environmental parameters by analogy to known pesticide compounds with similar molecular descriptors. This approach was evaluated via the identification of TPs of the triazole fungicide tebuconazole occurring in soil during a field dissipation study. Overall, 22 empirical and 12 yet unknown TPs were detected, and categorized into three groups with defined environmental properties. This approach combining suspect screening time-of-flight mass spectrometry with molecular typology could be extended to other organic pollutants and used to rationalize the choice of TPs to be investigated towards a more comprehensive environmental risk assessment scheme., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The performance of the pesticide fate model PRZM to predict the fate of two fungicides, penconazole and metalaxyl, and the major metabolite of metalaxyl (CGA-62826), in amended and unamended vineyard soils was tested from undisturbed soils columns experiments. Three different treatments were tested in two soils: control soil (unamended), and soil amended with fresh or composted spent mushroom substrates, which correspond to common agricultural practices in Spain. Leaching experiments were performed under non-saturated flow conditions. The model was parameterized with laboratory and literature data, and using pedotransfer functions. It was first calibrated for water flow against chloride breakthrough curves. The key parameter was the hydrodynamic dispersion coefficient (DISP). No leaching of penconazole, the most hydrophobic fungicide, was observed. It remained in the top 0-8 cm of the column. In any case, simulations were highly correlated to the experimental results. On the contrary, metalaxyl and its metabolite were consistently found in the leachates. A calibration step of the Kd of metalaxyl and CGA-62826 and of DISP for CGA-62826 was necessary to obtain good prediction of the leaching of both compounds. PRZM generally simulated acceptable metalaxyl vertical distribution in the soil profiles although results were overestimated for its metabolite. Nevertheless, PRZM can be reasonably used to assess the leaching (through breakthrough curves) and vertical distribution of fungicides in amended soils, knowing their DISP values., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A comprehensive review of quantitative structure-activity relationships (QSAR) allowing the prediction of the fate of organic compounds in the environment from their molecular properties was done. The considered processes were water dissolution, dissociation, volatilization, retention on soils and sediments (mainly adsorption and desorption), degradation (biotic and abiotic), and absorption by plants. A total of 790 equations involving 686 structural molecular descriptors are reported to estimate 90 environmental parameters related to these processes. A significant number of equations was found for dissociation process (pK a ), water dissolution or hydrophobic behavior (especially through the K OW parameter), adsorption to soils and biodegradation. A lack of QSAR was observed to estimate desorption or potential of transfer to water. Among the 686 molecular descriptors, five were found to be dominant in the 790 collected equations and the most generic ones: four quantum-chemical descriptors, the energy of the highest occupied molecular orbital (E HOMO ) and the energy of the lowest unoccupied molecular orbital (E LUMO ), polarizability (α) and dipole moment (μ), and one constitutional descriptor, the molecular weight. Keeping in mind that the combination of descriptors belonging to different categories (constitutional, topological, quantum-chemical) led to improve QSAR performances, these descriptors should be considered for the development of new QSAR, for further predictions of environmental parameters. This review also allows finding of the relevant QSAR equations to predict the fate of a wide diversity of compounds in the environment.

The ability of three models (PEARL, MACRO and PRZM) to describe the water transfer and leaching of the herbicides S-metolachlor and mesotrione as observed in an irrigated maize monoculture system in Toulouse area (France) was compared. The models were parameterized with field, laboratory and literature data, and pedotransfer functions using equivalent parameterization to better compare the results and the performance of the models. The models were evaluated and compared from soil water pressure, water content and temperature data monitored at 0.2, 0.5 and 1 m depth, together with water percolates and herbicide concentrations measured in a tension plate lysimeter at 1 m depth. Some hydraulic (n, θ(s)) parameters and mesotrione DT50 needed calibration. After calibration, the comparison of the results obtained by the three models indicated that PRZM was not able to simulate properly the water dynamic in the soil profile. On the contrary, PEARL and MACRO simulated generally quite well the observed water pressure head and volumetric water content at the three different depths during wetting periods (e.g. irrigated cropping period) while a poorest performance was obtained for drying periods (fallow period with bare soil and beginning of crop period). Similar water flow dynamics were simulated by PEARL and MACRO in the soil profile although in general, and due to a higher evapotranspiration in MACRO, PEARL simulated a wetter soil than MACRO. For the whole simulated period, the performance of all models to simulate water leaching at 1m depth was poor, with an overestimation of the total water volume measured in the lysimeter (ranging from 2.2 to 6.6 times). By contrast, soil temperature was properly reproduced by the three models. The models were able to simulate the leaching of herbicides at 1m depth in similar appearance time and order of magnitude as field observations. Cumulative observed and simulated mesotrione losses by leaching were consistently higher than the observed and simulated losses of the less mobile herbicide, S-metolachlor. In general, PRZM predicted the highest concentrations for both herbicides in the leachates while PEARL simulated the observed herbicide concentrations better than MACRO and PRZM., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Following legislation, the assessment of the environmental risks of 30000-100000 chemical substances is required for their registration dossiers. However, their behavior in the environment and their transfer to environmental components such as water or atmosphere are studied for only a very small proportion of the chemical in laboratory tests or monitoring studies because it is time-consuming and/or cost prohibitive. Therefore, the objective of this work was to develop a new methodology, TyPol, to classify organic compounds, and their degradation products, according to both their behavior in the environment and their molecular properties. The strategy relies on partial least squares analysis and hierarchical clustering. The calculation of molecular descriptors is based on an in silico approach, and the environmental endpoints (i.e. environmental parameters) are extracted from several available databases and literature. The classification of 215 organic compounds inputted in TyPol for this proof-of-concept study showed that the combination of some specific molecular descriptors could be related to a particular behavior in the environment. TyPol also provided an analysis of similarities (or dissimilarities) between organic compounds and their degradation products. Among the 24 degradation products that were inputted, 58% were found in the same cluster as their parents. The robustness of the method was tested and shown to be good. TyPol could help to predict the environmental behavior of a "new" compound (parent compound or degradation product) from its affiliation to one cluster, but also to select representative substances from a large data set in order to answer some specific questions regarding their behavior in the environment., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Introduction and Hypothesis: the aim of this study was to evaluate a link between mesh infection and shrinkage., Methods: twenty-eight Wistar rats were implanted with synthetic meshes that were either non-absorbable (polypropylene (PP), n = 14) or absorbable (poly (D: ,L: -lactic acid) (PLA94), n = 14). A validated animal incisionnal abdominal hernia model of mesh infection was used. Fourteen meshes (n = 7 PLA94 and n = 7 PP meshes) were infected intraoperatively with 10e6 CFU Escherichia coli, and compared with 14 non-infected meshes (n = 7 PLA94 and n = 7 PP meshes) (control groups). Explantations were performed on day 30. Shrinkage was evaluated by a reproducible numerical analysis of mesh area. Infection and histological study were evaluated on day 30., Results: non-infected meshes were less shrunk than infected meshes for both non-absorbable (5.0 ± 1.7% versus 21.6 ± 6.1%, p < 0.05) and absorbable meshes (2.4 ± 0.9% versus 11.0 ± 2.5%, p < 0.05)., Conclusion: this study highlights a link between infection and shrinkage in the model used.

The introduction of glyphosate-tolerant (GT) crops is expected to mitigate the environmental contamination by herbicides because glyphosate is less persistent and toxic than the herbicides used on non-GT crops. Here, we compared the environmental balances of herbicide applications for both crop types in three French field trials. The dynamic of herbicides and their metabolites in soil, groundwater and air was simulated with PRZM model and compared to field measurements. The associated impacts were aggregated with toxicity potentials calculated with the fate and exposure model USES for several environmental endpoints. The impacts of GT systems were lower than those of non-GT systems, but the accumulation in soils of one glyphosate metabolite (aminomethylphosphonic acid) questions the sustainability of GT systems. The magnitude of the impacts depends on the rates and frequency of glyphosate application being highest for GT maize monoculture and lowest for combination of GT oilseed rape and non-GT sugarbeet crops., (Copyright (c) 2010 Elsevier Ltd. All rights reserved.)

Following application, pesticides can be intercepted and absorbed by weeds and/or crops. Plants containing pesticides residues may then reach the soil during the crop cycle or after harvest. However, the fate in soil of pesticides residues in plants is unknown. Two commonly used foliar herbicides, glyphosate and sulcotrione, (14)C-labeled, were applied on leaves of oilseed rape and/or maize, translocation was studied, and then soil incubations of aerial parts of plants containing herbicides residues were performed. Soil treated directly with herbicides was used as control. The effects of adjuvants on herbicide plant-absorption and subsequent soil-degradation were also investigated comparing herbicides application as active ingredients and as commercial formulations. The fate in soil of herbicides residues in plants was different from that of control, and different for glyphosate and sulcotrione. Mineralization in soil of glyphosate in crops decreased compared to control, and amounts of (14)C-extractable residues, mainly composed by the metabolite aminomethylphosphonic acid (AMPA), and non-extractable residues (NER) increased. In contrast, mineralization in soil of sulcotrione in maize increased compared to control, with a decrease in the (14)C-extractable residues and an increase in NER. The fate of both herbicides was influenced by the type of plant organ in which herbicide was incorporated, because of differences in herbicides bioavailability and organs biodegradability, but not by adjuvants. Absorption of both herbicides in plant delays their subsequent soil-degradation, and particularly, glyphosate persistence in soil could increase from two to six times. The modifications of herbicide degradation in soil due to interception by plants should be considered for environmental risks assessment.

Background: Crops resistant to glyphosate may mitigate the increasing contamination of the environment by herbicides, since their weeding requires smaller amounts of herbicides and fewer active ingredients. However, there are few published data comparing the fate of glyphosate with that of substitute herbicides under similar soil and climatic conditions. The objectives of the work reported here were (i) to evaluate and compare the fate in soil in field conditions of glyphosate, as used on glyphosate-resistant oilseed rape, with that of two herbicides frequently used for weed control on the same crop, albeit non-resistant: trifluralin and metazachlor, and (ii) to compare field results with predictions of the pesticide root zone model (PRZM), parameterized with laboratory data. Dissipation and vertical distribution in the soil profile of glyphosate, trifluralin and metazachlor were monitored in an experimental site located in Eastern France for 1 year., Results: Herbicide persistence in the field increased as follows: metazachlor < glyphosate < trifluralin, contrary to laboratory results showing glyphosate to be least persistent. The main metabolite of glyphosate-aminomethylphosphonic acid (AMPA)-was more persistent than glyphosate. AMPA and trifluralin had the largest vertical mobility, followed by metazachlor and glyphosate. PRZM underestimated the dissipation rate of glyphosate in the field and the formation of AMPA, but its predictions for trifluralin and metazachlor were correct. The simulation of herbicides and AMPA distribution in the soil profile was satisfactory, but the mobility of trifluralin and metazachlor was slightly underestimated, probably because PRZM ignores preferential flow. In general, data from the laboratory allowed an acceptable parameterization of the model, as indicated by goodness-of-fit indices., Conclusion: Because of the detection of AMPA in the deep soil layer, the replacement of both trifluralin and metazachlor with glyphosate might not contribute to decreasing environmental contamination by herbicides. PRZM may be used to evaluate and to compare other weed control strategies for herbicide-resistant as well as non-resistant crops., ((c) 2008 Society of Chemical Industry.)

Use of glyphosate resistant crops was helpful in addressing observed increases in environmental contamination by herbicides. Glyphosate is a broad-spectrum herbicide, and its behaviour-as well as that of other herbicides-in soils is an important consideration for the overall environmental evaluation of genetically resistant crop introduction. However, few data have been published comparing glyphosate behaviour in soil to that of the herbicides that would be replaced by introduction of glyphosate resistant crops. This work compares glyphosate adsorption in soil with that of other herbicides frequently used in rape (trifluralin and metazachlor), sugarbeet (metamitron) and corn (sulcotrione). Herbicide adsorption was characterised in surface soils and in the complete soils profiles through kinetics and isotherms using batch equilibration methods. Pedological and molecular structure factors controlling the adsorption of all five herbicides were investigated. Glyphosate was the most strongly adsorbed herbicide, thus having the weakest potential for mobility in soils. Glyphosate adsorption was dependent on its ionisable structure in relation to soil pH, and on soil copper, amorphous iron and phosphate content. Trifluralin adsorption was almost equivalent to glyphosate adsorption, whereas metazachlor, metamitron and sulcotrione adsorption were lower. Trifluralin, metazachlor and metamitron adsorption increased with soil organic carbon content. Sulcotrione was the least adsorbed herbicide in alkaline soils, but its adsorption increased when pH decreased. Ranking the adsorption properties among the five herbicides, glyphosate and trifluralin have the lowest availability and mobility in soils, but the former has the broadest spectrum for weed control.

The introduction of crops resistant to the broad spectrum herbicide glyphosate, N-(phosphonomethyl)glycine, may constitute an answer to increased contamination of the environment by herbicides, since it should reduce the total amount of herbicide needed and the number of active ingredients. However, there are few published data comparing the fate of glyphosate in the environment, particularly in soil, with that of substitute herbicides. The objective of this study is to compare the fate of glyphosate in three soils with that of four herbicides frequently used on crops that might be glyphosate resistant: trifluralin, alpha,alpha,alpha-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine, and metazachlor, 2-chloro-N-(pyrazol-1-ylmethyl)acet-2',6'-xylidide for oilseed rape, metamitron, 4-amino-4,5-dihydro-3-methyl-6-phenyl-1,2,4-triazin-5-one for sugarbeet and sulcotrione, 2-(2-chloro-4-mesylbenzoyl)cyclohexane-1,3-dione for maize. The distribution of herbicides between the volatilized, mineralized, extractable and non-extractable fractions was studied, along with the formation of their metabolites in laboratory experiments using 14C-labelled herbicides, over a period of 140 days. The main dissipation pathways were mineralization for glyphosate and sulcotrione, volatilization for trifluralin and non-extractable residues formation for metazachlor and metamitron. The five herbicides had low persistence. Glyphosate had the shortest half-life, which varied with soil type, whereas trifluralin had the longest. The half-lives of metazachlor and sulcotrione were comparable, whereas that of metamitron was highly variable. Glyphosate, metazachlor and sulcotrione were degraded into persistent metabolites. Low amounts of trifluralin and metamitron metabolites were observed. At 140 days after herbicide applications, the amounts of glyphosate and its metabolite residues in soils were the lowest in two soils, but not in the third soil, a loamy sand with low pH. The environmental advantage in using glyphosate due to its rapid degradation is counterbalanced by accumulation of aminomethylphosphonic acid specifically in the context of extensive use of glyphosate., (Copyright 2005 Society of Chemical Industry)