Simple and rapid method for 336 multiresidual pesticide analysis in saliva, determination of their chemical stabilities, and biomonitoring of farmers. (December 2022)

• Record Type: Journal Article
• Authors: Park, Eunyoung; Lee, Jiho; Lee, Hye Suk; Kim, Jeong-Han; Shin, Yongho
• Is Part Of: Chemosphere. Volume 309:Part 1(2022)
• Publication Date: 2022-12
• Subjects: Saliva -- Pesticide -- Multiresidues -- QuEChERS -- Chemical stability -- Exposure; CE collision energy -- CID collision-induced dissociation -- dSPE dispersive solid-phase extraction -- EI electron ionization -- ESI electrospray ionization -- GCB graphitized carbon black -- ME matrix effect -- PSA primary secondary amine -- QC quality control -- QuEChERS quick, easy, cheap, effective, rugged, and safe -- S/N signal-to-noise ratio -- S/P saliva/plasma; Pollution -- Periodicals; Pollution -- Physiological effect -- Periodicals; Environmental sciences -- Periodicals; Atmospheric chemistry -- Periodicals; 551.511
• DOI: 10.1016/j.chemosphere.2022.136725
• Languages: English
• ISSNs: 0045-6535

Abstract

Abstract: Simultaneous multiresidual pesticide analysis of saliva samples was performed using scaled-down QuEChERS extraction with LC-MS/MS and GC-MS/MS. The optimum extraction procedure using acidified acetonitrile was applicable to 336 pesticides (287 for LC-MS/MS and 49 for GC-MS/MS). To determine pesticide multiresidues in saliva, 100 μL of the sample was extracted with 200 μL of 0.1% formic acid in acetonitrile, and the initial extract was partitioned with 40 mg of MgSO4 and 10 mg of NaCl. The organic supernatants (120 μL) were then mixed with acetonitrile (30 μL) for matrix-matching (4:1, v/v), and the final extract solution was injected into the LC-MS/MS (4 μL) and GC-MS/MS (2 μL) systems. The established analytical method showed a good LOQs between 5 and 25 ng/mL with reliable accuracy/precision values and recovery results (50–140%) for the target pesticides. Under the two different storage conditions, most of the analytes did not undergo chemical changes in the saliva samples, whereas some pesticides were more stable in freeze-thaw processes than those left at room temperature. Biomonitoring of farmers (ten mixers and ten sprayers) was successfully applied using the validated method, and two carbamates (fenobucarb and propamocarb) were determined at trace concentrations (12.5–675.0 ng/mL from 11 positively detected samples). Graphical abstract: Image 1 Highlights: A modified QuEChERS was developed for multiresidual pesticide analysis in saliva. Acidified acetonitrile exhibited excellent extraction efficiency for the target pesticides. Chemical stability of each pesticide was evaluated under two different conditions. It can be used for agricultural, forensic, and clinical purposes.