Dislodgeable Foliar Residue Measurements and Assessment of Dermal Exposure to Captan for Workers in Apple Orchards.

Captan dislodgeable foliar residues (DFRs) were determined by following the applications of this fungicide in an apple orchard. The study comprised an investigation of the variability of captan DFR values and 14 days of DFR monitoring to assess kinetic modeling. A method combining solid-phase microextraction (SPME) gas chromatography and high-resolution mass spectrometry (GC-QTOF-MS) was developed for the quantification of captan residues from DFR aqueous extracts. The results evidenced that (1) sampling parameters such as the position of the tree in a row and the height of foliar significantly influenced captan DFR levels (247-1450 ng·cm-2), highlighting the need to implement a comprehensive sampling strategy; (2) the DFR captan dissipation kinetic model best matched with a biphasic one, with half-lives of DFRcaptan of 3.4 and 12.8 days, respectively, for the initial rapid phase 1 decline (day 0-5) and the slower phase 2 decline phase (day 6-14). Furthermore, through DFR measurements, the potential dermal exposure (PDE) of workers was assessed using transfer coefficients (TCs) from the literature. Compared to the acceptable operator exposure levels (AOELs), the results showed that the re-entry interval for captan may not sufficiently protect workers whose arms, hands, and legs are not covered.

Pesticide exposure of workers in apple growing in France.

OBJECTIVE: Although apple trees are heavily sprayed, few studies have assessed the pesticide exposure of operators and workers in apple orchards. However, these data are crucial for assessing the health impact of such exposures. The aim of this study was to measure pesticide exposure in apple growing according to tasks and body parts. METHODS: A non-controlled field study was conducted in apple orchards in 4 regions of France during the 2016 and 2017 treatment seasons. Workers' external contamination and their determinants were assessed over 156 working days corresponding to 30 treatment days, 68 re-entry days and 58 harvesting days. We measured pesticide dermal contamination during each task and made detailed observations of work characteristics throughout the day. Captan and dithianon were used as markers of exposure. RESULTS: The median dermal contamination per day was 5.50 mg of captan and 3.33 mg of dithianon for operators, 24.39 mg of captan and 1.84 mg of dithianon for re-entry workers, and 5.82 mg of captan and 0.74 mg of dithianon for harvesters. Thus, workers performing re-entry tasks, especially thinning and anti-hail net opening, presented higher contamination, either equal to or higher than in operators. For these last ones, mixing/loading and equipment cleaning were the most contaminating tasks. Most of the contamination was observed on workers' hands in all tasks, except for net-opening in which their heads accounted for the most daily contamination. CONCLUSIONS: This study highlights the importance of taking indirect exposures into account during re-entry work in apple growing.

Pesticide Exposure of Residents Living in Wine Regions: Protocol and First Results of the Pestiprev Study.

The PESTIPREV study has been designed to investigate residential exposure to pesticides applied to vines and ultimately propose mitigation measures. A feasibility study was carried out to validate a protocol for measuring six pesticides in three houses located near vineyards in July 2020. Samples included indoor and outdoor surfaces sampled with wipes (n = 214), patches on the resident's skin (n = 7), hand or foot washing (n = 5), and pets sampled using wipes (n = 2). Limits of quantification for wipes ranged between 0.02 ng for trifloxystrobin and 1.50 ng for pyraclostrobin. Tebuconazole and trifloxystrobin were quantified in nearly 100% of the surface samples, whereas the other fungicides were less frequently found (from 39.7% for pyraclostrobin to 55.1% for boscalid). The median surface loadings ranged from 3.13 ng/m2 for benalaxyl to 82.48 ng/m2 for cymoxanil. The pesticides most frequently quantified in hand washing, patch samples, and pet wipes were the same as those quantified on surfaces. Finally, the analyses proved to be successful. The tools developed to collect information on determinants were well completed. The protocol was well received by the participants and appeared to be feasible and relevant to the objective of the PESTIPREV study, although some improvements have been identified. It was applied on a larger scale in 2021 to study the determinants of pesticide exposure.

Basis of a FTIR spectroscopy methodology for automated evaluation of Akt kinase inhibitor on leukemic cell lines used as model.

The PI3K/Akt-signaling pathway, associated with cancer development and disease progression, is recognized to be an anti-tumor drug target that could present important therapeutic benefit. However, no targeted Akt medicines have been commercialized yet, reflecting that drug selection procedures requires significant improvement from early research to clinical trials. Thus, new methods permitting both the evaluation of cytotoxic and proliferation inhibition effect on cancer cells but also to provide a global fingerprint of the drug action mechanism of new Akt inhibitor candidates are of major interest. Because it can detect very subtle molecular changes and could provide a global fingerprint of drug effects on cells, Fourier-transform infrared (FTIR) spectroscopy appears to be a promising method to develop new time- and cost-saving tools for chemical library screening improvements. In this study, we combine FTIR spectroscopy, advanced chemometrics analysis and cross-validation by standard biological assays to establish a basis of a mid-throughput methodology for rapid and automated assessment of cell response to Akt inhibitors and quantitative evaluation of their anti-proliferative effects. Our results shows that our methodology is able (1) to detect cell response to an Akt inhibitor exposure even for very low doses, (2) to provide biochemical information of interest about its effects on the cell metabolism, lipidome, and proteome, (3) to predict accurately resulting cell proliferation inhibition rate. Thus, further based on a large spectral data base, our methodology could contribute to facilitate preliminary screening of chemical libraries and improving the selection procedure of drug candidates in laboratory routine.

Kinetic and mechanistic investigations of progesterone reaction with ozone.

The removal of progesterone by ozone in aqueous solution was studied in this work. The absolute rate constant was evaluated and first by-products were identified. The reaction was studied in the 2.0-8.0 pH range and was found to be a second-order reaction, first-order relative to each compound concentration. The rate constant, determined by kinetic experiments in presence of an OH radical scavenger (tert-butanol), was independent of pH. The value was evaluated to be equal to 480+/-30 M(-1)s(-1) by two kinetic methods. Mass spectrometry analyses were performed to investigate primary degradation products generated by the reaction of ozone with progesterone. Two by-products were evidenced. According to these results, a degradation pathway of progesterone reacting with ozone was proposed.