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

Abstract

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.

Liquid Chromatography-Tandem Mass Spectrometry for the Simultaneous Analysis of 353 Pesticides in the Edible Insect Tenebrio molitor Larvae (Mealworms)

“…Therefore, this method is applicable but limited for screening of TCMTB. It has been reported that TCMTB exhibited higher recovery (70–120%) when using QuEChERS methods in crops and biological samples [ 46 , 47 ]. Thus, further studies of edible insects and livestock are required.…”

Analytical methods to analyze pesticides and herbicides

“…A linear range (1-250 ng/L), intra-and inter-day RSDs (2.31%-19.54% and 4.35%-27.15%, respectively), matrix effects (≤20% for most compounds), and recoveries within 55.54%-121.21% (RSD = 11.34%) were achieved. Shin et al (2019) developed scaled-down QuEChERS procedures using nonbuffer reagents for pesticide determination in human urine by LC-MS/MS. LOQ of 10 ng/ml and linearity of 10-250 ng/ml (R 2 ≥ 0.988) were obtained.…”

“…Shin et al (2019) developed scaled‐down QuEChERS procedures using nonbuffer reagents for pesticide determination in human urine by LC‐MS/MS. LOQ of 10 ng/ml and linearity of 10–250 ng/ml ( R 2 ≥ 0.988) were obtained.…”

Multiresidue screening of pesticides in Panax Ginseng C. A. Meyer by ultra‐high‐performance liquid chromatography with quadrupole time‐of‐flight mass spectrometry

“…Currently, tandem mass spectrometry (e.g., quadrupole TOF MS [Q‐TOF‐MS] and triple quadrupole MS [QqQ‐MS]) has become one of the preferred methods for pesticide residue analysis [20]. In particular, QqQ‐MS in multiple reaction monitoring (MRM) mode can detect target pesticides with sensitivity and selectivity [21]. However, the QqQ‐MS has several limitations.…”