Chiral method validation and stereoselective degradation of profoxydim isomers in paddy soil.

The herbicide profoxydim, which is chiral in nature, is commonly used for weed control in rice. However, traditional achiral analysis treats profoxydim isomers as a single compound, providing only partial and inaccuracy information assuming identical behavior for the four isomers. To address this issue, a sensitive and straightforward chiral analytical method was developed using QuEChERS and chiral HPLC-MS/MS to determine the residues of all four stereoisomers of profoxydim in soil.

Kinetic study, byproducts characterization and photodegradation pathway of profoxydim in a biochar water soil system.

The study focused on the photodegradation of profoxydim, a low-toxicity cyclohexanedione herbicide commonly used in rice crops, under simulated sunlight conditions. Profoxydim's behavior in paddy field conditions is not well understood, and this research aimed to fill that gap, particularly examining the effect of commonly utilized organic amendments such as biochar (BC) on its degradation. Results indicated that profoxydim degrades rapidly, with a half-life of 2.

Profoxydim in Focus: A Structural Examination of Herbicide Behavior in Gas and Aqueous Phases.

This study investigates the chemical structure of profoxydim, focusing on its E-isomer, the main commercial form. The research aimed to determine the predominant tautomeric forms under various environmental conditions. Using proton and carbon-13 NMR spectroscopy alongside theoretical modeling, we examined tautomers and their conformers in different solvents (MeOD, DMSO, CDCl, benzene) to mimic gas and aqueous phases.

Study of the different evaluation areas in the pesticide risk assessment process: Focus on pesticides based on microorganisms.

Both chemical and microbial active substances can currently be approved as pesticides in the EU, the provisions of their approval being set under Regulation (EC) No 1107/2009. Although sharing the same legal framework, chemicals and microorganisms used as pesticides have different risk profiles especially because once released into the environment, microbial active substances may produce secondary metabolites, multiply, spread and possibly genetically adapt or transfer antimicrobial resistance genes to other microorganisms. Consequently, the risk assessment process must adjust to the specificities ensuing from the chemical or microbial nature of the active substance.

A study using QSAR/QSPR models focused on the possible occurrence and risk of alloxydim residues from chlorinated drinking water, according to the EU Regulation.

Any active substance with phytosanitary capacity intended to be marketed in Europe must pass exhaustive controls to assess its risk before being marketed and used in European agriculture. Since the implementation of Regulation (EC) No 1107/2009, agrochemical companies have been obliged to study the formation of pesticide transformation products (TPs) during the treatment of drinking water containing pesticide residues. However, there is no consensus on how to address this requirement.

The toxic unit approach as a risk indicator in honey bees surveillance programmes: A case of study in Apis mellifera iberiensis.

The influence of genetic diversity and exposure to xenobiotics on the prevalence of pathogens was studied within the context of a voluntary epidemiological study in Spanish apiaries of Apis mellifera iberiensis, carried out during the spring season of years 2014 and 2015. As such, the evolutionary lineages of the honey bee colonies were identified, a multiresidue analysis of xenobiotics was carried out in beebread and worker bee samples, and the Toxic Unit (TUm) was estimated for each sampled apiary. The relationship between lineages and the most prevalent pathogens (Nosema ceranae, Varroa destructor, trypanosomatids, Black Queen Cell Virus; and Deformed Wing Virus) was analysed with contingency tables, and the possible relationships between TUm and the prevalence of these pathogens were studied by using a factor analysis.

Computational-Based Study of QuEChERS Extraction of Cyclohexanedione Herbicide Residues in Soil by Chemometric Modeling.

Assessment of two buffered QuEChERS (quick, easy, cheap, effective, rugged, and safe) versions (i.e., citrate and acetate) modified by including methanol to recover the residues of three cyclohexanedione oxime (CHD) herbicides and three of their byproducts from agricultural soil was performed.

Considerations of nano-QSAR/QSPR models for nanopesticide risk assessment within the European legislative framework.

The European market for pesticides is currently legislated through the well-developed Regulation (EC) No. 1107/2009. This regulation promotes the competitiveness of European agriculture, recognizing the necessity of safe pesticides for human and animal health and the environment to protect crops against pests, diseases and weeds.

Assessing the Effects of Alloxydim Phototransformation Products by QSAR Models and a Phytotoxicity Study.

Once applied, an herbicide first makes contact with leaves and soil. It is known that photolysis can be one of the most important processes of dissipation of herbicides in the field. However, degradation does not guarantee detoxification and can give rise to byproducts that could be more toxic and/or persistent than the active substance.

Computational Study of the Structure and Degradation Products of Alloxydim Herbicide.

Density functional theory calculations allowed us to study alloxydim herbicide and to identify the most stable conformers, the factors that governs their stability, and the interconversion mechanisms among the most relevant conformers. The degradation chain involves, as a first step, the cleavage of the N-O bond and the formation of a stable intermediate difficult to characterize experimentally. The study performed also allowed us to identify the properties of this elusive intermediate and to determine that the dominant fragmentation process in the gas phase is the homolytic fragmentation.

Photolysis of clethodim herbicide and a formulation in aquatic environments: Fate and ecotoxicity assessment of photoproducts by QSAR models.

The photochemical fate of the herbicide clethodim in natural waters was investigated under simulated and natural sunlight radiation. This herbicide exhibited a rapid degradation rate in simulated aquatic environment with half-lives ranged from 27.9min to 4.

The impact of restrictions on neonicotinoid and fipronil insecticides on pest management in maize, oilseed rape and sunflower in eight European Union regions.

Background: In 2013, the European Commission restricted the use of three neonicotinoids (clothianidin, imidacloprid and thiamethoxam) and the pyrazole fipronil, which are widely used to control early-season pests. Here, we used original farm survey data to examine the impact of the restrictions on pest management practices in eight regional case studies including maize, oilseed rape and sunflower in seven European Union (EU) countries.

Results: In four case studies, farmers switched to using untreated seeds as no alternative seed treatments were available.

Quantum chemistry in environmental pesticide risk assessment.

The scientific community and regulatory bodies worldwide, currently promote the development of non-experimental tests that produce reliable data for pesticide risk assessment. The use of standard quantum chemistry methods could allow the development of tools to perform a first screening of compounds to be considered for the experimental studies, improving the risk assessment. This fact results in a better distribution of resources and in better planning, allowing a more exhaustive study of the pesticides and their metabolic products.

Photodegradation behaviour of sethoxydim and its comercial formulation Poast under environmentally-relevant conditions in aqueous media. Study of photoproducts and their toxicity.

Photolysis is an important route for the abiotic degradation of many pesticides. However, the knowledge of the photolytic behaviour of these compounds and their commercial formulations under environmentally-relevant conditions are limited. The present study investigated the importance of photochemical processes on the persistence and fate of the herbicide sethoxydim and its commercial formulation Poast in aqueous media.

Development of a rapid and direct method for the determination of organic acids in peach fruit using LC-ESI-MS.

An accurate, simple and rapid liquid chromatography mass spectrometry method for the determination of organic acids in peach fruit has been developed. Direct injection and sample clean-up with a mixed-mode sorbent was compared. The best results for the determination of gluconic, oxalic, malic, citric and fumaric acids were obtained with only a simple dilution and filtration step, and nylon filters should be avoided since some organic acids are retained by them.

Aqueous photodegradation of sethoxydim herbicide: Qtof elucidation of its by-products, mechanism and degradation pathway.

The photochemical fate of sethoxydim herbicide in water was studied under simulated sunlight radiation (Suntest apparatus). This compound exhibited a rapid degradation rate in water with a half-life of approximately 1h, which is in accordance with the high calculated value of the quantum yield (Φ=0.26).

Biopesticides in the framework of the European Pesticide Regulation (EC) No. 1107/2009.

Background: The European Pesticide Regulation (EC) No. 1107/2009 encourages the use of less harmful active substances. Two main concerns involve the application of cut-off criteria for pesticides without losing tools for future agriculture (especially for minor uses) and the implementation of zonal evaluations.

Indirect photodegradation of clethodim in aqueous media. byproduct identification by quadrupole time-of-flight mass spectrometry.

Aqueous photolysis of clethodim herbicide in the presence of natural substances such as humic acids (HA), nitrate, and Fe(III) ions has been investigated. The photodegradation rate of clethodim was retarded in the presence of HA compared to ultrapure water, while nitrate ions had no effect. On the other hand, water containing different concentrations of Fe(III) ions enhanced degradation of this herbicide.

Field-incurred fenitrothion residues in kakis: comparison of individual fruits, composite samples, and peeled and cooked fruits.

Field trials have been carried out to determine the variability of residue levels of fenitrothion and its main metabolites fenitrothion-oxon and 3-methyl-4-nitrophenol in individual kaki fruits versus composite samples, in peel versus flesh, and in whole uncooked versus whole cooked fruits. Residue levels have been determined by gas chromatography with thermionic specific detection after extraction with ethyl acetate and without further cleanup. At harvest, residue levels of fenitrothion were below maximum residue levels (MRLs) and the two metabolites 3-methyl-4-nitrophenol and fenitrothion-oxon could be quantified with average amounts of 0.

Occurrence, Distribution, and Relative Incidence of Mosaic Viruses Infecting Field-Grown Melon in Spain.

The main areas for field-grown melon (Cucumis melo) production in Spain were surveyed for the occurrence and relative incidence of cucumber mosaic virus (CMV), papaya ringspot virus-watermelon strain (PRSV-W), watermelon mosaic virus-2 (WMV-2), and zucchini yellow mosaic virus (ZYMV) during the growing seasons of 1995 and 1996. Samples from 1,152 plants showing symptoms of virus infection were collected from commercial melon fields and analyzed by enzyme-linked immunosorbent assay (ELISA). CMV and WMV-2 were the most frequently found viruses, both by the number of locations and by their incidence in each location.