Characterization of trisiloxane surfactants from agrochemical adjuvants and pollinator-related matrices using liquid chromatography coupled to mass spectrometry.

Trisiloxane surfactants (TSSs) have been associated with honeybee learning impairment and the ongoing global bee decline. A liquid chromatography-mass spectrometry strategy for the identification of TSSs from agrochemical adjuvants and pollinator-related matrices is introduced here. The strategy incorporates chromatographic retention behavior, isotope ratio, reference to a compiled database of accurate masses, and TSS hydrolysis when necessary. Using this analytical strategy, three TSSs (x = 0, R = H, m = 1, 2, or 3) were identified for the first time from almond flowers of a commercial orchard. The three major purified TSS components in popularly used spray tank adjuvants were identified as TSS (x = 0, m = 0, R = H, CH3, or C(O)CH3) and their structures confirmed by nuclear magnetic resonance spectroscopy. These monitoring tools allow the assessment of the agricultural residues and potential risks of major TSS contaminants to important nontarget species such as honeybee and other essential pollinators.