色谱

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

• 研究论文 • 上一篇    下一篇

超高效液相色谱-串联质谱法检测动物源性食品中8种有机磷酸酯

唐艳1,2, 闻胜2, 曹文成2, 刘潇2, 雷承霖2,3, 程青云2, 陈海川2, 刘翎2, 刘小方2,*(), 周妍2,*()   

  1. 1.新疆大学生命科学与技术学院,新疆 乌鲁木齐 830017
    2.国家卫生健康委员会食品安全风险评估与标准研制特色实验室,湖北省疾病预防控制中心,湖北 武汉 430079
    3.湖北工业大学生命科学与健康工程学院,湖北 武汉 430079
  • 收稿日期:2024-07-11 出版日期:2025-04-08 发布日期:2025-03-26
  • 通讯作者: *E-mail:zy_hbcdc@163.com(周妍); E-mail:13971689391@163.com(刘小方).
  • 基金资助:
    国家重点研发计划(2023YFF1104800);湖北省自然科学基金项目(2022CFB022);湖北省自然科学基金项目(2023AFB1012);湖北省自然科学基金项目(2024AFB526);湖北省卫生健康委科研资助(WJ2023M106)

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)

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摘要： 采用乙腈作为提取溶剂,结合超声波辅助萃取和SPE柱进行前处理,建立了超高效液相色谱-串联质谱测定动物源性食品中8种有机磷酸酯(OPEs)的检测方法。准确称取0.5 g样品,用5 mL乙腈超声萃取;冷冻离心后取上清液,用HMR-Lipid SPE柱进行净化,待测分析物经C18色谱柱分离,在正离子模式下采集,2,2-二(氯甲基)-1,3-丙二醇双[双(2-氯乙基)磷酸酯]酯(V6)采用外标法定量,其他7种化合物(磷酸三乙酯(TEP)、磷酸三丙酯(TPrP)、磷酸三丁酯(TnBP)、磷酸三(2-氯乙基)酯(TCEP)、磷酸三(2-氯丙基)酯(TCIPP)、磷酸三(1,3-二氯-2-丙基)酯(TDCIPP)和磷酸三苯酯(TPHP))采用内标法定量。结果表明,该方法线性相关系数r2≥0.9900;各物质检出限为0.01~0.87 μg/kg,定量限为0.02~2.62 μg/kg;在2、20、100 μg/kg 3个水平下进行加标回收试验,回收率为80.5%~117.8%; RSD≤14.8%(n=6)。按此方法分析了12种动物源性食品样品(草鱼、鲈鱼、小龙虾、牛乳、奶粉、酸奶、猪肉、牛肉、鸡肉、鸭肉、鸡蛋和鸭蛋),其中化合物TnBP和TCIPP的检出率为100%, TEP、TCEP、TPHP和TDCIPP的检出率高于50%, TPrP和V6未检出。本方法前处理操作简单,分析速度快,回收率和精密度较好,适用于多种动物源性食品中OPEs的快速分析检测。

关键词: 有机磷酸酯, 动物源性食品, 超高效液相色谱-串联质谱

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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