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Pesticides use raises concerns regarding environmental sustainability, as pesticides are closely linked to the decline of biodiversity and adverse human health outcomes. This study proposed a holistic approach for assessing the potential risks posed by pesticides for human health and the environment in the eastern region of Michoacan, where extensive agricultural lands, especially corn and avocado fields, surround the Monarch Butterfly Biosphere Reserve. We used a combination of qualitative (semi-structured interviews) and quantitative (chemical analysis) data. Fifty-five interviews with smallholder farmers allowed us to identify pesticide types, quantities, frequencies, and application methods. A robust and precise analytical method based on solid-phase extraction and LC-MS/MS was developed and validated to quantify 21 different pesticides in 16 water samples (rivers, wells, runoff areas). We assessed environmental and human health risks based on the pesticides detected in the water samples and reported in the interviews. The interviews revealed the use of 28 active ingredients, including glyphosate (29 % of respondents), imidacloprid (27 %), and benomyl (24 %). The pesticide analysis showed the presence of 13 different pesticides and degradation products in the water samples. The highest concentrations were found for imidacloprid (1195 ngL -1 ) and carbendazim (a degradation product of benomyl; 932 ngL -1 ), along with the metabolite of pyrethroid insecticides, 3-PBA (494 ngL -1 ). The risk assessment indicates that among the most used pesticides, the fungicide benomyl and carbendazim pose the highest risk to human health and aquatic ecosystems, respectively. This study unveils novel insights on agricultural practices for the avocado, a globally consumed crop that is undergoing rapid production expansion. It calls for the harmonisation of crop protection with environmental responsibility, safeguarding the health of the people involved and the surrounding ecosystems., 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 Elsevier B.V. All rights reserved.)

Various pharmaceuticals are essential for livestock farming, but some are highly toxic to aquatic life if they reach surface water bodies. Mediterranean Climate is characterized by dry summers followed by intense autumn storms. We studied the effect of these climatic conditions on the risk of pharmaceutical residues transfer to streams at the catchment-scale. Pharmaceutical products routinely used in the study area, as well as their application frequency and season, were identified through interviews with farmers. As a proof a concept, three veterinary pharmaceuticals (Fenbendazole (FBZ), Mebendazole (MBZ) and Ivermectin (IVM)) were chosen as model chemicals based on their relatively high usage, their specificity to represent different types of livestock (swine, sheep and cattle), and their ability to be analyzed using the same analytical method. Stream water was analyzed during low flow periods and at high frequency (up to 2 h -1 ) during flood events. The selected veterinary pharmaceuticals were not detected during low flow, but FBZ and MBZ reached high concentrations for short periods during floods. Due to the event-driven nature of their transfer, a significant load of veterinary pharmaceuticals can reach the river and cause temporary but significant degradation of water quality (e.g. for FBZ, the water concentration reached up to 355 times the predicted no effect concentration (PNEC)). This indicates that special care should be taken to avoid keeping freshly treated livestock on pastures that may become hydrologically connected under wet conditions. In addition, it suggests that low-frequency monitoring is not sufficient to detect those high concentration levels that exist during very short 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 © 2023 Elsevier B.V. All rights reserved.)

Up till now, the diclofenac (DCF) transformation into its nitrogen-derivatives, N-nitroso-DCF (NO-DCF) and 5-nitro-DCF (NO2-DCF), has been mainly investigated in wastewater treatment plant under nitrification or denitrification processes. This work reports, for the first time, an additional DCF microbial mediated nitrosation pathway of DCF in soil under strictly anoxic conditions probably involving codenitrification processes and fungal activities. This transformation pathway was investigated by using field observations data at a soil aquifer system (Katari watershed, Bolivia) and by carrying out soil slurry batch experiments. It was also observed for diphenylamine (DPA). Field measurements revealed the occurrence of NO-DCF, NO2-DCF and NO-DPA in groundwater samples at concentration levels in the 6-68s/L range. These concentration levels are more significant than those previously reported in wastewater treatment plant effluents taking into account dilution processes in soil. Interestingly, the p-benzoquinone imine of 5-OH-DCF was also found to be rather stable in surface water. In laboratory batch experiments under strictly anoxic conditions, the transformation of DCF and DPA into their corresponding N-nitroso derivatives was well correlated to denitrification processes. It was also observed that NO-DCF evolved into NO2-DCF while NO-DPA was stable. In vitro experiments showed that the Fisher-Hepp rearrangement could not account for NO2-DCF formation. One possible mechanism might be that NO-DCF underwent spontaneous NO loss to give the resulting intermediates diphenylaminyl radical or nitrenium cation which might evolve into NO2-DCF in presence of NO2 radical or nitrite ion, respectively., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.