Application of mid-infrared spectroscopy to the prediction and specification of pesticide sorption: A promising and cost-effective tool.

The cocktail of pesticides sprayed to protect crops generates a miscellaneous and generalized contamination of water bodies. Sorption, especially on soils, regulates the spreading and persistence of these contaminants. Fine resolution sorption data and knowledge of its drivers are needed to manage this contamination. The aim of this study is to investigate the potential of Mid-Infrared spectroscopy (MIR) to predict and specify the adsorption and desorption of a diversity of pesticides. We constituted a set of 37 soils from French mainland and West Indies covering large ranges of texture, organic carbon, minerals and pH. We measured the adsorption and desorption coefficients of glyphosate, 2,4-dichlorophenoxyacetic acid (2,4-D) and difenoconazole and acquired MIR Lab spectra for these soils. We developed Partial Least Square Regression (PLSR) models for the prediction of the sorption coefficients from the MIR spectra. We further identified the most influencing spectral bands and related these to putative organic and mineral functional groups. The prediction performance of the PLSR models was generally high for the adsorption coefficients Kdads (0.4 < R2 < 0.9 & RPIQ >1.8). It was contrasted for the desorption coefficients and related to the magnitude of the desorption hysteresis. The most significant spectral bands in the PLSR differ according to the pesticides indicating contrasted interactions with mineral and organic functional groups. Glyphosate interacts primarily with polar mineral groups (OH) and difenoconazole with hydrophobic organic groups (CH2, CC, COO-, C-O, C-O-C). 2,4-D has both positive and negative interactions with these groups. Finally, this work suggests that MIR combined with PLSR is a promising and cost-effective tool. It allows both the prediction of adsorption and desorption parameters and the specification of these mechanisms for a diversity of pesticides including polar active ingredients.

Potential of fluorescent tracers to appraise biochar amendment strategies for pesticide mitigation - insights from comparative sorption.

Mitigation of pesticide dispersion in soil and water is required to protect ecosystem health and the anthropic uses of water bodies. Biochar amendments have been suggested to reduce pesticide dispersion due to their high sorption potentials. Nevertheless, appraisals at different scales have been limited by the costs of pesticide analyses. The aim of this study was to evaluate the potential of two fluorescent tracers, uranine (UR) and sulforhodamine B (SRB), for use as pesticide proxies in the context of biochar amendments used for mitigation purposes. Therefore, we compared the sorption processes of both fluorescent tracers and those of three pesticides, glyphosate, 2,4-D, and difenoconazole for soils; three wood biochars (pine, oak, and beech/charm blend); and soil/biochar mixtures representing agricultural usages. The results showed that the sorption of glyphosate by soil was unaffected by amendment with the tested pine, oak, and wood blend biochars. In contrast, the sorption coefficients of UR, SRB, 2,4-D, and difenoconazole were significantly increased with these biochar amendments. SRB, in particular, exhibited sorption behavior similar to that of the hydrophobic fungicide difenoconazole. This indicates promise for the use of SRB as a proxy for hydrophobic pesticides, in testing biochar amendments.

Flow patterns and pathways of legacy and contemporary pesticides in surface waters in tropical volcanic catchments.

Severe water pollution issues due to legacy and contemporary pesticides exist in tropical regions and are linked to cash crops requiring intensive plant protection practices. This study aims to improve knowledge about contamination routes and patterns in tropical volcanic settings to identify mitigation measures and analyse risk. To this aim, this paper analyses four years of monitoring data from 2016 to 2019 of flow discharge and weekly pesticide concentrations in the rivers of two catchments grown predominantly with banana and sugar cane in the French West Indies. The banned insecticide chlordecone, applied in banana fields from 1972 to 1993, was still the major source of river contamination, while the currently used herbicide glyphosate, its metabolite aminomethylphosphonic acid (AMPA), and postharvest fungicides also exhibited high contamination levels. A value of 0.5 of the Gustafson Ubiquity Score (GUS) was shown to separate contaminant and noncontaminant pesticides, indicating a high vulnerability to pollution by pesticides in this tropical volcanic context. The patterns and routes of river exposure to pesticides differed markedly between the pesticides in accordance with the hydrological behaviour of volcanic islands and the history and nature of pesticide uses. Concerning chlordecone and its metabolites, observations confirmed previous findings of a main subsurface origin of river contamination by this compound but also showed large erratic short-term variations, suggesting the influence of fast surface transport processes such as erosion for legacy pesticides with large sorption capacity. Concerning herbicides and postharvest fungicides, observations have suggested that surface runoff and fast lateral flow in the vadose zone control river contamination. Accordingly, mitigation options need to be considered differently for each type of pesticide. Finally, this study points out the need for developing specific exposure scenarios for tropical agricultural contexts in the European regulation procedures for pesticide risk assessment.

Soil metabolomics: A powerful tool for predicting and specifying pesticide sorption.

Sorption regulates the dispersion of pesticides from cropped areas to surrounding water bodies as well as their persistence. Assessing the risk of water contamination and evaluating the efficiency of mitigation measures, requires fine-resolution sorption data and a good knowledge of its drivers. This study aimed to assess the potential of a new approach combining chemometric and soil metabolomics to estimate the adsorption and desorption coefficients of a range of pesticides. It also aims to identify and characterise key components of soil organic matter (SOM) driving the sorption of these pesticides. We constituted a dataset of 43 soils from Tunisia, France and Guadeloupe (West Indies), covering extensive ranges of texture, organic carbon and pH. We performed untargeted soil metabolomics by liquid chromatography coupled with high-resolution mass spectrometry (UPLC-HRMS). We measured the adsorption and desorption coefficients of three pesticides namely glyphosate, 2,4-D and difenoconazole for these soils. We developed Partial Least Square Regression (PLSR) models for the prediction of the sorption coefficients from the RT-m/z matrix and conducted further ANOVA analyses to identify, annotate and characterise the most significant constituents of SOM in the PLSR models. The curated metabolomics matrix yielded 1213 metabolic markers. The prediction performance of the PLSR models was generally high for the adsorption coefficients Kdads (0.3 < R2 < 0.8) and for the desorption coefficients Kfdes (0.6 < R2 < 0.8) but low for ndes (0.03 < R2 < 0.3). The most significant features in the predictive models were annotated with a confidence level of 2 or 3. The molecular descriptors of these putative compounds suggest that the pool of SOM compounds driving glyphosate sorption is reduced compared to 2,4-D and difenoconazole, and these compounds are generally more polar. This approach can provide estimates of the adsorption and desorption coefficients of pesticides, including polar pesticide, for contrasted pedoclimates.

Is a dissipation half-life of 5 years for chlordecone in soils of the French West Indies relevant?

Recently, Comte et al. (2022) re-examined the natural degradation of chlordecone (CLD) in the soils of the French West Indies (FWI) by introducing an additional 'dissipation parameter' into the WISORCH model developed by Cabidoche et al. (2009). Recent data sets of CLD concentrations in FWI soils obtained by Comte et al. enabled them optimizing the model parameters, resulting in significantly shorter estimates of pollution persistence than in the original model. Their conclusions jeopardize the paradigm of a very limited degradation of CLD in FWI soils, which may lead to an entire revision of the management of CLD contamination. However, we believe that their study is questionable on several important aspects. This includes potential biases in the data sets and in the modeling approach. It results in an inconsistency between the estimated dissipation half-life time (DT50) of five years that the authors determined for CLD and the fate of CLD in soil from the application period 1972-1993 until nowadays. Most importantly, a rapid dissipation of CLD in the field as proposed by Comte et al. is not sufficiently supported by data and estimates. Hence, the paradigm of long-term persistence of CLD in FWI soils is still to be considered.

Evaluation of temperature corrections for pesticide half-lives in tropical and temperate soils.

Temperature is a key factor that influences pesticide degradation. Extrapolating degradation half-lives (DT50) measured at a given temperature to different temperatures remains challenging, especially for tropical conditions with high temperatures. In this study, the use of the standard Arrhenius equation for correcting temperature effects on pesticide degradation in soils was evaluated and its performance was compared with that of alternative Arrhenius-based equations. To do so, a database of 509 DT50 values measured between 5 and 35 °C for 32 pesticides on tropical and temperate soils was compiled for the first time through an extensive literature search. The temperature correction models were fitted to the database using linear mixed regression approaches that included soil type and compound effects. No difference in the temperature dependence of DT50 between tropical and temperate soils was detected, regardless of the model. A comparison of the prediction performances of the models showed that constant activation energy (Ea) cannot be considered valid for the whole range of temperatures. The classical Arrhenius equation with an Ea of 65.4 kJ.mol-1, as recommended by the European Food Safety Authority (EFSA), was shown to be valid for correcting the DT50 only for temperatures ranging from 5 to 20 °C. However, for temperatures greater than 20 °C, which are common in tropical environments, the median Ea was significantly lower at 10.3 kJ.mol-1. These findings suggest the need to adapt the standard temperature correction of the European pesticide risk assessment temperature procedure when it is applied in tropical settings.

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

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

Evaluating SoilGen2 as a tool for projecting soil evolution induced by global change.

To protect soils against threats, it is necessary to predict the consequences of human activities and global change on their evolution on a ten to hundred year time scale. Mechanistic modelling of soil evolution is then a useful tool. We analysed the ability of the SoilGen model to be used for projections of soil characteristics associated to various soil threats: vertical distributions of <2µm fraction, organic carbon content (OC), bulk density and pH. This analysis took the form of a functional sensitivity analysis in which we varied the initial conditions (parent material properties) and boundary conditions (co-evolution of precipitation and temperature; type and amount of fertilization and tillage as well as duration of agriculture). The simulated scenario variants comprised anthroposequences in Luvisols at two sites with one default scenario, six variants for initial conditions and 12 variants for boundary conditions. The variants reflect the uncertainties to our knowledge of parent material properties or reconstructed boundary conditions. We demonstrated a sensitivity of the model to climate and agricultural practices for all properties. We also conclude that final model results are not significantly affected by the uncertainties of boundary conditions for long simulations runs, although influenced by uncertainties on initial conditions. The best results were for organic carbon, although improvements can be reached through calibration or by incorporating a dynamic vegetation growth module in SoilGen. Results were poor for bulk density due to a fixed-volume assumption in the model, which is not easily modified. The <2µm fraction depth patterns are reasonable but the process of clay new formation needs to be added to obtain the belly shape of the Bt horizon. After calibration for organic carbon under agriculture, the model is suitable for producing soil projections due to global change.