A Quantitative Tandem Mass Spectrometry and Scaled-Down QuEChERS Approach for Simultaneous Analysis of Pesticide Multiresidues in Human Urine

• Published in: Molecules (Basel, Switzerland) Vol. 24; no. 7; p. 1330
• Main Authors: Shin, Yongho, Lee, Jiho, Park, Eunyoung, Lee, Junghak, Lee, Hye Suk, Kim, Jeong-Han
• Format: Journal Article
• Language: English
• Published: Switzerland MDPI AG 04.04.2019; MDPI
• Subjects: Biomonitoring; Calibration; Chromatography; Correlation coefficient; Correlation coefficients; forensic; Forensic science; Human wastes; Ionization; LC-MS/MS; Liquid chromatography; Magnesium sulfate; Mass spectrometry; Mass spectroscopy; Methods; multiresidue; pesticide; Pesticides; Poisoning; Prevention; Quantitation; QuEChERS; Reagents; Scientific imaging; Sodium chloride; Solvents; Spectroscopy; Urine; LC-MS/MS; multiresidue; forensic; urine; pesticide; QuEChERS
• ISSN: 1420-3049; 1420-3049
• DOI: 10.3390/molecules24071330

Multiresidual pesticide determination in a biological sample is essential for an immediate decision and response related to various pesticide intoxications. A rapid and simultaneous analytical method for 260 pesticides in human urine was developed and validated using liquid chromatography-tandem mass spectrometry (LC-MS/MS). High speed positive/negative switching electrospray ionization (ESI) mode was used, and scheduled multiple reaction monitoring (MRM) was optimized. Three versions of scaled-down QuEChERS procedures were evaluated, and the procedure using non-buffer reagents (magnesium sulfate and sodium chloride) and excluding cleanup steps was selected for optimum pesticide extraction. The limit of quantitation (LOQ) in this methodology was 10 ng/mL for each target pesticide, and correlation coefficient (r²) values of calibration curves were ≥0.988 (linearity range; 10-250 ng/mL). In accuracy and precision tests, the relative error ranges were -18.4% to 19.5%, with relative standard deviation (RSD) 2.1%-19.9% at an LOQ level (10 ng/mL), and -14.7% to 14.9% (RSD; 0.6%-14.9%) at higher concentrations (50, 150, and 250 ng/mL). Recovery range was 54.2%-113.9% (RSD; 0.3%-20.0%), and the soft matrix effect (range; -20% to 20%) was observed in 75.4% of target pesticides. The established bioanalytical methods are sufficient for application to biomonitoring in agricultural exposures and applicable in the forensic and clinic.