Determination of diquat and paraquat in water by liquid chromatography-(electrospray ionization) mass spectrometry

Abstract

A method for the determination of the herbicides diquat and paraquat in water was developed using liquid chromatography-(electrospray ionization) mass spectrometry [LC-(ESI)MS]. The analytes were isolated on an ENVI-8 DSK solid phase extraction (SPE) disk and eluted with 5-M trifluoroacetic acid (TFA). The eluate was evaporated to dryness and the analytes were redissolved in the mobile phase (7% methanol/93% water/25-mM TFA). The extract was analyzed by liquid chromatography (C1 column) with postcolumn addition of propionic acid/methanol followed by (ESI)MS. Diquat was detected using the [M(2+)-H+] ion (M2+ = dication) at m/z 183, whereas paraquat was detected using the mono-trifluoroacetate ion pair [M2 +/- OOCCF3] at m/z 299. Quantitation was done by isotope dilution mass spectrometry using d4-diquat and d8-paraquat and the corresponding ions [M(2+)-D+] and [M2 +/- OOCCF3] at m/z 186 and m/z 307, respectively. Detection limits of 0.1 and 0.2 microgram/L, respectively (based on the dications), were adequate to meet the Ontario Drinking Water Objectives of 70 and 10 micrograms/L, respectively, and the Ontario Provincial Water Quality Objective for diquat of 0.5 microgram/L. Precision and accuracy were 14% and 6% for diquat and 12% and 3% for paraquat.