Pentafluorobenzylation and detection of sodium monofluoroacetate (compound 1080) in veterinary samples using gas chromatography/tandem quadrupole mass spectrometry with multiple reaction monitoring

Abstract

The analytical detection of chemical residues from sodium monofluoroacetate (MFA) ingestion in targeted predatory wildlife and in pesticide misuse incidents perpetrated against nuisance companion animals remains a concern in veterinary forensic toxicology. There is a current need for chemically stable sample extracts with reliable and specific diagnostic methods for trace quantities in diverse diagnostic matrices. Methods: Biphasic pentafluorobenzylation provided a simple combined extraction and derivatization procedure for removing MFA in a chemically stable form from a complex matrix such as stomach contents. Analysis of the derivatized extract using gas chromatography/tandem quadrupole mass spectrometry (GC/MS/MS) with multiple reaction monitoring (MRM) approaches specific to MFA provided greater specificity than simple scan or selected ion monitoring approaches. Results: Collision-induced dissociation in GC/MS/MS showed that pentafluorobenzyl (PFB)-derivatized MFA (M + m/z 258) generated m/z 258à130, 149, 161, 177, 178, 180.1, and 181.1 transitions. Of these, the transition m/z 258à181 provided a peak for quantitation, whereas m/z 258à161 and 258à178 provided specificity for qualifying MFA. Similarly, PFB-derivatized 2-chloropropionic acid (M + m/z 288) was used as an internal standard, which generated m/z 288à181 and 161. Of these, the transition m/z 288à181 provided a peak for quantitation, whereas m/z 288à161 and 181à161 served to qualify the internal standard. Conclusions: The method was validated with a calculated limit of detection of 0.35 ppm and limit of quantitation of 1.09 ppm MFA. The method should have adequate sensitivity and reliability for veterinary toxicology labs analyzing specimens from animals poisoned by this predacide.