Chinese Journal of Chromatography ›› 2025, Vol. 43 ›› Issue (4): 309-316.DOI: 10.3724/SP.J.1123.2024.07010

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Determination of eight organophosphate esters in animal-derived foods by ultra performance liquid chromatography-tandem mass spectrometry

TANG Yan1,2, WEN Sheng2, CAO Wencheng2, LIU Xiao2, LEI Chenglin2,3, CHENG Qingyun2, CHEN Haichuan2, LIU Ling2, LIU Xiaofang2,*(), ZHOU Yan2,*()   

  1. 1. College of Life Sciences and Technology, Xinjiang University, Urumqi 830017, China
    2. NHC Specialty Laboratory of Food Safety Risk Assessment and Standard Development, Hubei Provincial Center for Disease Control and Prevention, Wuhan 430079, China
    3. School of Life and Health Sciences, Hubei University Of Technology, Wuhan 430079, China
  • Received:2024-07-11 Online:2025-04-08 Published:2025-03-26
  • Supported by:
    National Key Research and Development Program of China(2023YFF1104800);Hubei Provincial Natural Science Foundation of China(2022CFB022);Hubei Provincial Natural Science Foundation of China(2023AFB1012);Hubei Provincial Natural Science Foundation of China(2024AFB526);Hubei Province Health and Family Planning Scientific Research Project(WJ2023M106)

Abstract:

Organophosphate esters (OPEs) are widely used as flame retardants in most regions, they adversely affect ecosystems and threaten human health. OPEs have attracted significant public attention because they are toxic and ubiquitously present in the environment. While China is among the world’s largest users and producers of OPEs, limited data on the exposure of animal-derived foods to OPEs exist; consequently, a method for quantifying OPEs in animal-derived food samples is needed.

In this study, a method was developed for the determination of eight OPEs, including triethyl phosphate (TEP), tripropyl phosphate (TPrP), tri-n-butyl phosphate (TnBP), tris(2-chloroethyl) phosphate (TCEP), tris(2-chloroisopropyl) phosphate (TCIPP), tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), triphenyl phosphate (TPHP), and 2,2-bis(chloromethyl) trimethylene bis[bis(2-chloroethyl) phosphate] (V6), from twelve types of typical animal-derived foods by ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). The samples were purified using an HMR-Lipid SPE column. The effects of mobile phase A (water, 5 mmoL/L ammonium acetate aqueous solution, and 0.1% formic acid aqueous solution) and mobile phase B (methanol and acetonitrile), as well as the methanol/acetonitrile ratio on the separation and extraction efficiencies for the eight OPEs were investigated using one-way analysis. The results showed that optimal response values and peak shapes were obtained for the various compounds using 0.1% formic acid aqueous solution-acetonitrile system as the mobile phase. The following pretreatment procedure was used: A 0.5 g sample was accurately weighed and ultrasonically extracted with 5 mL of acetonitrile. The supernatant was collected after freezing and centrifugation, and cleaned-up was performed using an HMR-Lipid SPE column. The target analytes were analyzed using a Waters Acquity BEH C18 column (100 mm×2.1 mm, 1.7 μm) and ESI+ MS conditions. Compound V6 was quantified by the external standard method, with the other seven compounds quantified using the internal standard method. The method exhibited linearity with r2≥0.9900, limits of detection (LODs) of 0.01-0.87 μg/kg, and limits of quantification (LOQs) of 0.02-2.62 μg/kg for the various substances. Spiked recoveries of the eight OPEs at three levels (2, 20, and 100 μg/kg) were in the range of 80.5%-117.8% and RSDs ≤ 14.8% (n=6). Twelve animal-derived foods (grass carp, bass, Procambarus clarkii, milk, milk powder, yogurt, pork, beef, chicken, duck meet, egg, and duck egg) were analyzed using the developed method. Compounds TnBP and TCIPP were detected at rates of 100%, and TEP, TCEP, TPHP, and TDCIPP at rates greater than 50%, while TPrP and V6 were not detected. The method has a simple-to-operate pre-treatment step, analyzes rapidly with good recoveries and precisions, and is suitable for rapidly analyzing and detecting eight OPEs in a variety of animal-derived foods.

Key words: organophosphate esters (OPEs), animal-derived foods, ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)

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