Tracing the dissipation of difenoconazole, its metabolites and co-formulants in tomato: A comprehensive analysis by chromatography coupled to high resolution mass spectrometry in laboratory and greenhouse trials.

The study evaluated Ceremonia 25 EC®, a plant protection product (PPP) containing difenoconazole, in tomato crops, to identify potential risks associated with PPPs, and in addition to this compound, known metabolites from difenoconazole degradation and co-formulants present in the PPP were monitored. An ultra high performance liquid chromatography coupled to quadrupole-Orbitrap mass analyser (UHPLC-Q-Orbitrap-MS) method was validated with a working range of 2 µg/kg (limit of quantification, LOQ) to 200 µg/kg. Difenoconazole degradation followed a biphasic double first-order in parallel (DFOP) kinetic model in laboratory and greenhouse trials, with high accuracy (R2 > 0.9965). CGA-205374, difenoconazole-alcohol, and hydroxy-difenoconazole metabolites were tentatively identified and semi-quantified in laboratory trials by UHPLC-Q-Orbitrap-MS from day 2 to day 30. No metabolites were found in greenhouse trials. Additionally, 13 volatile co-formulants were tentatively identified by gas chromatography (GC) coupled to Q-Orbitrap-MS, detectable up to the 7th day after PPP application. This study provides a comprehensive understanding of difenoconazole dissipation in tomatoes, identification of metabolites, and detection of co-formulants associated with the applied PPP.

Uncovering the Dissipation of Chlorantraniliprole in Tomatoes: Identifying Transformation Products (TPs) and Coformulants in Greenhouse and Laboratory Studies by UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS.

The present study addressed the dissipation of the insecticide chlorantraniliprole in tomatoes treated with Altacor 35 WG under laboratory and greenhouse conditions, as well as the identification of transformation products (TPs) and coformulants, performing suspect screening analysis. Analyses were performed by ultra-high-performance liquid and gas chromatography coupled to quadrupole-Orbitrap high-resolution mass spectrometry (UHPLC-Q-Orbitrap-MS and GC-Q-Orbitrap-MS). In all cases, chlorantraniliprole was fitted to a biphasic kinetic model, with R2 values greater than 0.99. Dissipation was noticeably faster in greenhouse studies, in which even 96% dissipation was achieved over 53 days. One TP, IN-F6L99, was tentatively identified in both greenhouse and laboratory studies and was semiquantified by using chlorantraniliprole as the analytical standard, yielding a top value of 354 µg/kg for laboratory studies, whereas values for greenhouse studies fell under the limit of quantitation (LOQ). Finally, a total of 15 volatile coformulants were identified by GC-Q-Orbitrap-MS.

Assessment of Co-Formulants in Marketed Plant Protection Products by LC-Q-Orbitrap-MS: Application of a Hybrid Data Treatment Strategy Combining Suspect Screening and Unknown Analysis.

The aim of this study was the determination of co-formulants in 15 different chlorantraniliprole- and difenoconazole-based plant protection products (PPPs) belonging to different formulations. Samples were analyzed by ultrahigh-performance liquid chromatography coupled to Q-Orbitrap high-resolution mass accuracy spectrometry (UHPLC-Q-Orbitrap-MS), operating in full-scan MS and data-dependent acquisition (ddMS2) modes. A total of 78 co-formulants were tentatively identified by a combination of suspect screening and unknown analysis. Nine of them were later confirmed by analytical standards. Finally, the analytical method was successfully validated and co-formulants were quantified. Linear alkyl ethoxylates (LAS) were the most common type of co-formulant, followed by sodium alkylbenzene sulfonates. Moreover, sodium dodecyl benzene sulfonate had the highest concentration of any co-formulant (up to 32.33 g/L). In all, an innovative identification of co-formulants in a large number of PPPs is presented, which will give room for future studies delving into the composition of PPPs or determining these co-formulants in environmental or agricultural samples.

Co-formulants in plant protection products: An analytical approach to their determination by gas chromatography-high resolution mass accuracy spectrometry.

In the present study, 12 volatile benzene and naphthalene derived co-formulants were identified by suspect screening and unknown analysis in 14 plant protection products (PPPs) corresponding to several types of formulations, as emulsifiable concentrates (EC), suspension concentrates (SC), dispersible concentrates (DC) and ZC, which is a mixture of a capsule suspension (CS) in an SC, containing either difenoconazole or chlorantraniliprole as main active ingredients. The selected technique was gas chromatography coupled to Q-Orbitrap high resolution mass accuracy spectrometry (GC-Q-Orbitrap-MS), providing efficient separation and detection of all identified compounds. Finally, 42 compounds were tentatively identified, and 12 of them were confirmed and quantified using analytical standards. Results showed that the applied methodology was able to detect these co-formulants at concentrations as low as 0.03 g/L (tert-butylbenzene), encompassing a wide concentration range, up to 9.63 g/L (pentamethylbenzene). Pentamethylbenzene was the only compound detected in all studied samples.