Determination of 16 organophosphate esters in human blood by high performance liquid chromatography-tandem mass spectrometry combined with liquid-liquid extraction and solid phase extraction

• DOI: 10.3724/sp.j.1123.2020.07033
• Publication Date: 2021-10-25T08:34:15Z
• Authors: Minmin HOU; Yali SHI; Yaqi CAI
• Keywords: Solid phase extraction; Human blood; Dichloromethane

Measurement of organophosphate esters (OPEs) in human body fluids is important for understanding internal exposure to OPEs and assessing related health risks. Most the current studies have focused on determination OPE metabolites urine, as are readily metabolized into their diester or hydroxylated forms body. However, given existence one metabolite across multiple OPE, well low metabolic rates several vitro studies, reliability urinary biomarkers specific needs be treated with caution.Human blood a matrix that contact all organs tissues, levels compounds may better represent doses reach target tissues. Currently, only few investigated occurrence by different analytical methods, variety considered limited. In this study, method based liquid chromatography-tandem mass spectrometry (LC-MS/MS) was developed simultaneous 16 blood, extraction efficiency solid phase (SPE) column verified. To samples, 10 ng an standard added, followed mixing aging 30 min. The samples were extracted three times acetonitrile using shaker, then purified ENVI-18 cartridges containing 25% dichloromethane eluent. Finally, analyzed high performance spectrometry. After optimization mobile phases, analytes separated BEH C18 (100 mm×2.1 mm, 1.7 μm) gradient elution methanol 5 mmol/L ammonium acetate water phase. Then, ionized electrospray ionization positive (ESI+) mode detected reaction monitoring (MRM) mode. spectral parameters, including precursor ion, product declustering potential, entrance collision cell exit optimized. results quantified method. limits detection (LOD, S/N=3) range 0.0038-0.882 ng/mL. calibration curves showed good linear relationships 0.1-50 ng/mL, correlation coefficients >0.995. validated, average recoveries 54.6%-104%. (n=3) 15 OPEs, except trimethyl phosphate (TMP), whole at spiked 53.1%-126%, relative deviations (RSDs) 0.15%-12.6%. six standards 66.8%-91.6% TMP-d9 (39.1%), RSDs 3.52%-6.85%. effects 56.4%-103.0%. Significant found resorcinol bis(diphenyl phosphate) (RDP) (75.8%±1.4%), trimethylphenyl (TMPP) (68.4%±1.0%), 2-ethylhexyl di-phenyl (EHDPP) (56.4%±12.4%), bisphenol-A (BABP) (58.5%±0.4%). these could corrected similar signal suppressions corresponding (TPHP-d15, 77.4%±7.5%). This simple, highly sensitive, suitable blood. Fifteen collected quantify total concentrations ranged from 1.50 7.99 frequencies eight higher than 50%. Tri-iso-butyl (TiBP), tri(2-chloroethyl) (TCEP), tri(1-chloro-2-propyl) (TCIPP) dominant median 0.813, 0.764, 0.690 respectively. These indicated widespread which should concern.