Application of gas and liquid chromatography-mass spectrometry to the evaluation of pirimiphos methyl degradation products in industrial water under ozone treatment.

The organophosphorus compound pirimiphos methyl was oxidized in water under ozonolysis in the presence of formulating agents. A rapid sample handling procedure was developed based on liquid-solid extraction with nonporous carbon cartridges. This sorbent material allowed recovery of the polar degradation products (DPs). Analysis of oxidized solutions was performed with both GC-ion trap (IT)-MS using either electron impact or chemical ionization as ionization modes and LC-atmospheric pressure ionization (API)-MS using either an ionspray (ISP) or an atmospheric pressure chemical ionization (APCI) interface in order to confirm the presence of DPs. The performances of both technologies were evaluated for structure elucidation and quantitation by using pirimiphos methyl, 2,4-aminophenol and cyanuric acid as external standards of DPs. LC-API-MS techniques allowed the detection of six DPs, of which two were not detected by GC-IT-MS techniques, even after a derivatization procedure with BF3-MeOH reagent. ISP was the most suitable ionization method for identifying the DPs, because sodium or potassium adduct ions were of great help in confirming the molecular mass of unknowns. APCI provided more fragmentation patterns than ISP. However unequivocal identification of all DPs was impossible and only a tentative degradation pathway of pirimiphos methyl in water under ozone is proposed. At the end of the reaction time, DPs accounted for between 70 and 85% of the initial concentration of methyl pirimiphos.