Trace level determination of selected organophosphorus pesticides and their degradation products in environmental air samples by liquid chromatography-positive ion electrospray tandem mass spectrometry

This paper describes a new analytical method for determination of organophosphorus pesticides (OPs) along with their degradation products involving liquid chromatography (LC) positive ion electrospray (ESI+) tandem mass spectrometry (MS-MS) with selective reaction monitoring (SRM). Chromatography was performed on a Gemini C6-Phenyl (150 mmx2.0 mm, 3 microm) with a gradient elution using water-methanol with 0.1% formic acid, 2 mM ammonium acetate mobile phase at a flow rate of 0.2 mL min(-1). The LC separation and MS/MS operating conditions were optimized with a total analysis time less than 40 minutes. Method detection limits of 0.1-5 microg L(-1) for selected organophosphorus pesticides (OP), OP oxon degradation products, and other degradation products: 3,5,6-trichloro-2-pyridinol (TCP); 2-isopropyl-6-methyl-4-pyrimidol (IMP); and diethyl phosphate (DEP). Some OPs such as fenchlorphos are less sensitive (MDL 30 microg L(-1)). Calibration curves were linear with coefficients of correlation better than 0.995. A three-point identification approach was adopted with area from first selective reaction monitoring (SRM) transition used for quantitative analysis, while a second SRM transition along with the ratio of areas obtained from the first to second transition are used for confirmation with sample tolerance established by the relative standard deviation of the ratio obtained from standards. This new method permitted the first known detection of OP oxon degradation products including chlorpyrifos oxon at Bratt's Lake, SK and diazinon oxon and malathion oxon at Abbotsford, BC in atmospheric samples. Atmospheric detection limits typically ranged from 0.2-10 pg m(-3).