Quantitative determination of pesticides in human plasma using bio-SPME-LC-MS/MS: a robust tool to assess occupational exposure to pesticides

Analysis of biofluids, such as plasma, can be used to investigate occupational pesticide exposure in the agricultural industry. Considering the chemical complexity and variability of plasma samples, any protocol for pesticide analysis should achieve efficient sample cleanup to minimize matrix effects and enhance method sensitivity through analyte pre-concentration. In this work, a high-throughput method was developed for analysis of 79 pesticides, commonly used in agricultural practices, in human plasma, using biocompatible solid-phase microextraction (SPME) coupled to liquid chromatography-tandem mass spectrometry. An SPME method was developed using a biocompatible hydrophilic-lipophilic balance/polyacrylonitrile (HLB/PAN) extraction phase and demonstrated negligible matrix effects. The performance of the developed SPME method was compared to a QuEChERS -Quick, Easy, Cheap, Effective, Rugged, and Safe- method, the most common sample preparation and cleanup approach for pesticide analysis in complex matrices. Comparable accuracy and precision were achieved for both methods, with accuracy values within 70-120% and relative standard deviation < 15%. Overall, the developed SPME and QuEChERS methods extracted 79 out of 82 monitored pesticides in human plasma. The SPME protocol demonstrated higher sensitivity than the QuEChERS method and a drastic reduction of matrix effects.