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Metabolic transformation products of pesticides by electrochemical cell coupled to LC-MS (EC-LC-MS)
(2016)
Metabolic transformation products (TPs) of the insecticide chlorpyrifos (CPF), the new fungicide fluopyram (FLP) and the broad-spectrum herbicide, glyphosate (GLP), were studied by electrochemistry coupled to mass spectrometry (EC-MS) for the first time. Phase I metabolites of the three pesticides from rat liver in-vitro assay experiments were studied by LC-MS/MS and compared to electrochemically oxidized products from EC-MS.
Known metabolites from S-oxidation, O-dealkylation and hydroxylation of the insecticide chlorpyrifos have been identified by EC-MS and simulated to in-vitro assays. Chlorpyrifos-oxon (CPF-oxon), diethylthiophosphate (DETP), 3,5,6-trichloropiridinol (TCP), diethylphosphate (DEP) and 2,3,5-trichloropyridine (TCPy) were the main EC oxidative TPs and in-vitro assay metabolites of CPF which was also reported by Choe et al.. Fluopyram was extensively converted to a number of electrochemical products including mono- and dihydroxylated derivatives and yet unidentified TPs. Rat liver microsomal assay experiments showed mainly hydroxylated metabolites of FLP which was also reported by the European Food Safety Agency (EFSA). Aminomethyl phosphonic acid (AMPA) was the main TP of glyphosate detected from both EC-MS analysis and in-vitro assay tests.
A number of TPs of CPF, FLP and GLP have been identified by electrochemistry online mass spectrometry and compared to in-vitro assays. Using electrochemistry upfront MS enables fast and matrix free prediction of metabolic pathways, transformation products and/or fate of pesticides. Further studies will focus on structural characterization of detected compounds, phase II metabolites and investigation of real samples.
Bisphenol A (BPA) is widely used in many Polymers. Many outdoor applications are made from BPA-based materials which are exposed to a variety of environmental impacts, like temperature, solar radiation, rain, and others. This could lead to damaging and aging of the material which might cause leaching or migration of pollutants into the environment. To understand the fate and behavior different transformation products of selected Bisphenols will be generated and analyzed.