Determination of Residual Carbamate, Organophosphate, and Phenyl Urea Pesticides in Drinking and Surface Water by High-Performance Liquid Chromatography/Tandem Mass Spectrometry

Abstract

Methods using SPE followed by HPLC/MS/MS analysis were developed and validated for the determination of 39 pesticides in different aquatic environmental matrixes. The target pesticides included 12 carbamates, 15 organophosphates, and 12 phenyl ureas, out of which 16 are regulated in North America. Method detection limits were in the low ng/L range using the U.S. Environmental Protection Agency's protocol and multiple reaction monitoring (MRM) data acquisition, meeting the regulatory needs in the United States, Canada, and European Union. Isotope-labeled compounds were used as injection internal standards, as well as method surrogates to improve the data quality. QC/QA data (e.g., method recovery and within-run and between-run method precision) derived from multiyear monitoring activities were used to demonstrate method ruggedness. The same QC/QA data also showed that the method exerted no obvious matrix effect on the target analytes. Parameters that affect method performance, such as preservatives, pH values, sample storage time, and sample extract storage time, were also studied in detail. Accredited by the Canadian Association for Laboratory Accreditation and licensed by the Ontario government for drinking water analysis, these methods have been applied to the analysis of drinking water, ground water, and surface water samples collected in the province of Ontario, Canada, to ensure the pristine nature of Ontario's aquatic environment. Using the scheduled MRM (sMRM) data acquisition algorithm, it was demonstrated that sMRM improved the S/N of extracted ion chromatograms by at least two- to six-fold and, therefore, enhanced the short- and long-term instrument precision, demonstrated the ability to offer high throughput multiresidue analysis, and allowed the use of two MRM transitions for each compound to achieve higher confidence for compound identification.