High-throughput biomonitoring of organophosphate flame-retardant metabolites in urine via 96-blade solid-phase microextraction coupled with ultra-performance liquid chromatography-tandem mass spectrometry

Organophosphate flame retardants (OPFRs) are widely used in consumer products and building materials, but their propensity for migration poses a problem with respect to polluting indoor environments, water, soil, and dust. OPFR metabolites in urine samples are appropriate biomarkers for assessing exposure risk levels. In this paper, a high-throughput method that couples 96-blade solid-phase microextraction with ultra-performance liquid chromatography-tandem mass spectrometry (SPME-UPLC-MS/MS) is applied for the simultaneous detection of four OPFR metabolites in urine samples. The results indicated that the best extraction was achieved using 96 blades coated with hydrophilic-lipophilic balance weak anion exchange (HLB-WAX). The proposed SPME method's extraction efficiency was maximized by optimizing extraction time, pH value, desorption solution, desorption volume, and desorption time, and it was validated in accordance with the Food and Drug Administration's guidelines. The findings indicated that the proposed method has a wide linearity range (0.5-100 ng mL(-1)) and low detection limits (0.09-0.14 ng mL(-1)). The method's accuracy ranged from 98% to 118%, with intra-day precision ranging from 1% to 10%. In contrast, inter-day precision ranged from 3% to 16%. Accuracy was also evaluated using independent urine samples, which ranged from 78% to 124% with corresponding relative standard deviations (1%-16%). Ultimately, DoCP was detected in two real samples at a concentration of 0.5-1.1 ng mL(-1), and BEHP was detected at a concentration of 0.2-1.2 ng mL(-1). Overall, the proposed SPME-UPLC-MS/MS method is reliable, accurate, and capable of simultaneously determining four OPFR metabolites in urine samples and screening them to assess exposure risk for humans.