Rapid and sensitive analytical procedure for biomonitoring of organophosphate pesticide metabolites in human urine samples using a vortex‐assisted salt‐induced liquid–liquid microextraction technique coupled with ultra‐high‐performance liquid chromatography/tandem mass spectrometry

Abstract

Rationale Organophosphate pesticides (OPPs) are the most commonly used insecticides around the world in various agricultural and domestic practices, and humans are frequently exposed to these hazardous insecticides that can lead to several chronic health effects. Therefore, a fast and sensitive analytical method is required for biomonitoring the markers of OPPs in humans for exposure estimation. In this study, a fast and sensitive analytical procedure was developed for the determination of the metabolites of OPPs in human urine samples. Methods Metabolites of OPPs were extracted from 2 mL of urine sample using a novel vortex‐assisted salt‐induced liquid–liquid microextraction (VA‐SI‐LLME) technique, and the preconcentrated metabolites were analyzed by ultra‐high‐performance liquid chromatography/tandem mass spectrometry (UHPLC/MS/MS). Various factors affecting the efficiency of VA‐SI‐LLME were thoroughly investigated. Results The metabolites of OPPs exhibited very good linearity over the concentration range between 0.05 and 50 ng mL−1 with coefficient (r2) values ranging between 0.9986 and 0.9999. The method showed excellent sensitivity with detection limits ranging from 0.01 to 0.03 ng mL−1 and quantification limits from 0.03 to 0.05 ng mL−1. The developed method was applied to the analysis of real samples and the recoveries ranged between 85.0 and 114.1% with related standard deviations <5%. Conclusions The results showed the VA‐SI‐LLME/UHPLC/MS/MS method to be a simple, rapid, sensitive, and selective analytical procedure for the biomonitoring of the metabolites of OPPs in humans. This efficient and cost‐effective analytical method could be a potential alternative method for the biomonitoring of the metabolites of pesticides in humans.

Development and Validation of a New UFLC–MS/MS Method for the Detection of Organophosphate Pesticide Metabolites in Urine

“…The detection of DAP metabolites was made possible by a rapid and straightforward liquid-liquid extraction procedure. In contrast to previous studies, which required 0.5-10 mL of sample and 5-15 mL of solvent for sample extraction, the recovery rate was lower (13-114%) and chromatographic separation was lengthy (10-35 min), with a detection limit of 0.1-6 ng/mL [17,33,37,[40][41][42][43][44][45][46]. With the present method, each sample can be analyzed in only 30 min, making it ideal for laboratories that process a large volume of samples in a short time.…”

Development and validation of a novel UFLC-MS/MS method for the detection of biomarkers of organophosphate pesticide metabolites in urine.

“…In Table 5 Comparison of the proposed method with other reported methods. We compared our method with previously reported LC-MS /MS methods and their sample preparation [34][35][36][37][38][39] . This study showed the best extraction procedure for the determination of six OPs metabolites in the urine; we compared the extraction procedure commonly used and also compared the other reported LC-MS/MS method with our method, Our method proved to be more sensitive with detection limits between 0.0201 to 0.0697 ng/mL for all analytes.…”

Determination of pesticide residues in urine by chromatography-mass spectrometry: methods and applications

“…Alternatively, LLE with diethyl ether and ethyl acetate, alongside salting-out assisted extraction with MgSO 4 and NaCl, also adopting HILIC chromatography but with a Hypersil Gold HILIC column, was assessed for the same 6 DAPs ( 95 ). In a separate investigation, five DAPs were determined using VALLME with ethyl acetate and (NH 4 ) 2 SO 4 , however employing an Inspire C18 column for separation ( 96 ).…”