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A simple method for simultaneous determination of organophosphate esters and their diester metabolites in dairy products and human milk by using solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry

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Abstract

Organophosphate esters (OPEs) and their diester metabolites have been frequently found in various environmental matrices and regarded as emerging environmental pollutants, whereas data on their occurrence in foods and human matrices are still limited. In this study, a novel and simple procedure was developed to simultaneously determine 14 OPEs and 6 diester metabolites in dairy products and human milk. After enzymatic hydrolysis by β-glucuronidase/arylsulfatase, a freeze-dried milk sample was extracted with acetonitrile and purified by solid-phase extraction. Subsequently, all target compounds were determined by HPLC-ESI-MS/MS. Linearity, limits of detection (LODs), recovery, precision, and matrix effects of the proposed methodology were validated, and the parameters of HPLC-ESI-MS/MS were optimized. LODs for OPEs and their diester metabolites were from 0.001 to 0.02 ng/mL, and limits of quantification (LOQs) were 0.01–0.3 ng/mL. Average recoveries at two spiked levels ranged between 67.3 and 121%, with relative standard deviation lower than 20.7%. A test for matrix effects showed that most analytes presented signal suppression, and isotopically labeled ISs were essential for compensating for the matrix effects. Finally, OPEs and their metabolites both showed high detecting frequencies in real samples, which indicated that these emerging pollutants were ubiquitous in foods and the human body, and the impact of the diester metabolites on population exposure must be included in exposure assessment.

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Funding

This study was supported by the Capital’s Funds for Health Improvement and Research (CFH, No. 2022-2G-4264) and Project of “Practical Training Plan” (College Students Scientific Training Plan Project of Beijing Colleges and Universities High-level Talents Cross-Cultivation, No. 0700-12101314).

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Authors and Affiliations

  1. School of Public Health and Beijing Key Laboratory of Environmental Toxicology, Capital Medical University, Beijing, 100069, China

    Xuelei Chen, Ning Chen & Zhixiong Shi

  2. Beijing Center for Disease Prevention and Control, Beijing Research Center for Preventive Medicine, Beijing, 100013, China

    Nan Zhang, Liping Li, Rong Zhao & Sai Fan

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  1. Xuelei Chen
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  2. Nan Zhang
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Correspondence to Sai Fan or Zhixiong Shi.

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Human milk collection in our study has been approved by the Ethics Committee of the Capital Medical University.

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Chen, X., Zhang, N., Li, L. et al. A simple method for simultaneous determination of organophosphate esters and their diester metabolites in dairy products and human milk by using solid-phase extraction coupled to liquid chromatography-tandem mass spectrometry. Anal Bioanal Chem 414, 4255–4265 (2022). https://doi.org/10.1007/s00216-022-04079-3

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