Investigations into pesticide charge site isomers using conventional IM and cIM systems

A growing number of pesticides are being used around the world necessitating strict regulatory policies to guarantee consumer safety. Liquid Chromatography - Mass Spectrometry (LC-MS) is a highly sensitive method for pesticide screening, which provides retention time, mass/charge ratios and the relative abundances of characteristic product ions. Variability in the latter necessitates relatively large tolerances (+/- 30%, SANCO/ 12682/2019, current EU regulation). One cause of this variability may stem from the presence of different charge-site isomers (charge carrier being a proton, sodium cation, potassium cation and alike); each yielding a set of different product ions, of which the relative ratios are influenced by solution and ion source conditions. Consequently, varying relative abundances may be observed for analyte ions produced from calibration standards, chemical residues in food matrices and across different instruments. Ion Mobility Spectrometry (IMS) is a fast, gas phase separation technique which can resolve charge-site isomers based on differences in their collisional cross sections (CCSs). We previously used the IM device embedded in LC-IM-MS geometry to generate a pesticide CCS database and subsequently focussed upon identification of pesticides which form charge-site isomers. Latterly, we applied this approach to screen food commodities for pesticide residues. In some instances, isomer separation was clear, however sometimes broad, unresolved distributions were observed. Using a highresolution cyclic IM device (cIM) we resolved and determined CCS values of species of indoxacarb, spinosad, fenpyroximate, epoxiconazole, metaflumizone and avermectin. Furthermore, utilising novel cIM functionalities (tandem-IM) we discovered that two spinosyn sodimers can interconvert in the gas phase.