Liquid chromatography time-of-flight mass spectrometry evaluation of fungicides reactivity in free chlorine...

Liquid chromatography (LC) combined with tandem mass spectrometry (MS/MS), based on the use of a hybrid quadrupole-time-of-flight mass analyzer, was used to investigate the reactivity of nine fungicides in free chlorine-containing water samples. Three of the selected compounds (fenhexamid, FEN; pyrimethanil, PYR; and cyprodinil, CYP) displayed a poor stability in presence of moderate chlorine levels; thus, the effects of different parameters on their half-lives (t(1/2)) were evaluated. Sample pH, bromide traces, and the water matrix affected their relative stabilities. Despite such variations, the three fungicides are degraded at significant rates not only in ultrapure, but also in surface water spiked with chlorine levels up to 2 µg ml(-1), and when mixed with chlorinated tap water, generating several transformation products (TPs). The time-course of precursor species and their TPs was followed in the LC-MS mode, using the information contained in accurate, full scan mass spectra (MS) to propose the empirical formulae of TPs. Thereafter, their ion product scan (MS/MS) spectra were considered to set their chemical structures; allowing, in some cases, to distinguish between isomeric TPs. The reaction pathway of FEN, the less stable fungicide, involved just an electrophilic substitution of hydrogen per chlorine, or bromine, and cleavage of the molecule to render an amide. PYR and CYP shared common reaction routes consisting of halogenation, hydroxylation, and condensation processes leading to complex mixtures of TPs, which were relatively stable to further transformations.