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Tembotrione (TBT) is a β-triketone herbicide targeting the 4-Hydroxyphenylpyruvate dioxygenase enzyme (4-HPPD) of weeds. This molecule can also affect soil microorganisms, either through both direct and indirect toxic effects for microorganisms expressing 4-HPPD, or by promoting tolerant and/or degrading microbial populations. Our study aimed to characterize the impacts of TBT on the diversity of total- and hppd (coding for 4-HPPD) -soil bacterial communities. Soil microcosms were treated with the active ingredient TBT at the recommended field dose (100 g a.i/ha; D1) or the tenfold dose (D10). Soil samples were collected from 0 to 55 days post-treatment to study: (i) total- and hppd-bacterial diversities using 16SrRNA and hppd amplicons sequencing, respectively; (ii) TBT dissipation in soil. Both total- and hppd-bacterial community composition was not affected by TBT treatments (D1 and D10). However, D10 treatment slightly increased richness and phylogenetic diversity of the total bacterial community while decreasing hppd richness. Overall, the highest dose of TBT seemed to promote TBT-tolerant or TBT-degrading bacterial populations and to deplete TBT-sensitive ones. These effects were transient as TBT was rapidly dissipated with a DT 50 of 7 days and 15 days for D1 and D10, respectively. Differential abundance analysis with a Generalized Linear Model allowed the identification of Sphingomonas, Steroidobacter and Lysobacter as genus that were influenced by TBT, and which could be used as a new class of exposure biomarkers., 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.)

Conventional agriculture still relies on the general use of agrochemicals (herbicides, fungicides and insecticides) to control various pests (weeds, fungal pathogens and insects), to ensure the yield of crop and to feed a constantly growing population. The generalized use of pesticides in agriculture leads to the contamination of soil and other connected environmental resources. The persistence of pesticide residues in soil is identified as a major threat for in-soil living organisms that are supporting an important number of ecosystem services. Although authorities released pesticides on the market only after their careful and thorough evaluation, the risk assessment for in-soil living organisms is unsatisfactory, particularly for microorganisms for which pesticide toxicity is solely considered by one global test measuring N mineralization. Recently, European Food Safety Authority (EFSA) underlined the lack of standardized methods to assess pesticide ecotoxicological effects on soil microorganisms. Within this context, there is an obvious need to develop innovative microbial markers sensitive to pesticide exposure. Biomarkers that reveal direct effects of pesticides on microorganisms are often viewed as the panacea. Such biomarkers can only be developed for pesticides having a mode of action inhibiting a specific enzyme not only found in the targeted organisms but also in microorganisms which are considered as "non-target organisms" by current regulations. This review explores possible ways of innovation to develop such biomarkers for herbicides. We scanned the herbicide classification by considering the mode of action, the targeted enzyme and the ecotoxicological effects of each class of active substance in order to identify those that can be tracked using sensitive microbial markers., (Copyright © 2019. Published by Elsevier B.V.)

The emergence of pesticides of natural origin appears as an environmental-friendly alternative to synthetic pesticides for managing weeds. To verify this assumption, leptospermone, a natural β-triketone herbicide, and sulcotrione, a synthetic one, were applied to soil microcosms at 0× (control), 1× or 10× recommended field dose. The fate of these two herbicides (i.e. dissipation and formation of transformation products) was monitored to assess the scenario of exposure of soil microorganisms to natural and synthetic herbicides. Ecotoxicological impact of both herbicides was explored by monitoring soil bacterial diversity and activity using next-generation sequencing of 16S rRNA gene amplicons and soil metabolomics. Both leptospermone and sulcotrione fully dissipated over the incubation period. During their dissipation, transformation products of natural and synthetic β-triketone were detected. Hydroxy-leptospermone was almost completely dissipated by the end of the experiment, while CMBA, the major metabolite of sulcotrione, remained in soil microcosms. After 8 days of exposure, the diversity and structure of the soil bacterial community treated with leptospermone was significantly modified, while less significant changes were observed for sulcotrione. For both herbicides, the diversity of the soil bacterial community was still not completely recovered by the end of the experiment (45 days). The combined use of next-generation sequencing and metabolomic approaches allowed us to assess the ecotoxicological impact of natural and synthetic pesticides on non-target soil microorganisms and to detect potential biomarkers of soil exposure to β-triketones., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study presents a novel approach for assessing the risk of agrochemicals in soil microcosms through the use of non-targeted metabolomics. The metabolome of treated soils was extracted and tested through LCMS profiling in order to generate an "Environmental Metabolic Footprint" (EMF). A dynamic characterization of pollution biomarkers was obtained through a multivariate statistical analysis of EMF data, where our results show the possible evolution towards a state of resilience. The EMF methodology was applied to two β-triketone herbicides in soil microcosms: one natural, leptospermone, and one synthetic, sulcotrione. In spite of a four-fold higher application dose, leptospermone exhibited a lower resilience time than did sulcotrione (ca. 30 days vs ca. 45 days respectively)., (Copyright © 2016 Elsevier B.V. All rights reserved.)

The photolytic behaviour of tembotrione, a new chemical herbicide intended for foliar application in corn, was investigated under unnatural and extreme photochemical exposure in aqueous solutions in the laboratory. It appeared that degradation was dependent on pH and occurred more rapidly under acidic and neutral conditions, leading predominantly to the formation of a xanthenedione type compound by intramolecular cyclisation with loss of HCl. Trace amounts of benzoic acid by-products appeared also during UV-C irradiation (λ=254 nm) of the parent compound. Results were comparable to those obtained with sulcotrione, another β-triketone herbicide. These extreme irradiation conditions clearly accelerated the phototransformation of sulcotrione vs. simulated sunlight irradiation. Furthermore, the photolysis of the degradation by-products, resulting from either photolysis, hydrolysis or biotic pathways of the two active ingredients, was also carried out. The benzoic acid by-products appeared more stable to photolysis than their parent molecules. Xanthenedione derivatives were degraded more rapidly with several differences depending on the pH value., (Copyright © 2013 Elsevier B.V. All rights reserved.)