色谱

色谱 ›› 2020, Vol. 38 ›› Issue (8): 953-960.DOI: 10.3724/SP.J.1123.2020.01016

• 研究论文 • 上一篇    下一篇

固相萃取-气相色谱-串联质谱法检测水中18种酚类化合物

李杨1,2, 张书芬2, 邢家溧2,*(), 应璐2, 承海2, 郑睿行2, 毛玲燕2, 李和生1,*()   

  1. 1 宁波大学食品与药学学院, 浙江 宁波 315211
    2 宁波市食品检验检测研究院, 浙江 宁波 315048
  • 收稿日期:2020-01-21 出版日期:2020-08-08 发布日期:2020-12-11
  • 通讯作者: 邢家溧,李和生
  • 作者简介:李和生.E-mail:lihesheng@nbu.edu.cn
    邢家溧.E-mail:nbsjy2017@163.com;
  • 基金资助:
    国家市场监管总局科技计划项目(2019MK080);浙江省基础公益研究计划项目(LGC20C200013);宁波市现代服务业项目(2019F1017);宁波市自然科学基金项目(2019A610438);宁波市自然科学基金项目(2019A610437);宁波市自然科学基金项目(2018A610223);宁波市自然科学基金项目(2018A610336);宁波市泛3315创新团队(2018B-18-C);宁波市高新精英创新团队(甬高科[2018]63号)

Determination of 18 phenolic compounds in water by gas chromatography-tandem mass spectrometry coupled with solid phase extraction

LI Yang1,2, ZHANG Shufen2, XING Jiali2,*(), YING Lu2, CHENG Hai2, ZHENG Ruihang2, MAO Lingyan2, LI Hesheng1,*()   

  1. 1 College of Food and Pharmaceutical Sciences, Ningbo University, Ningbo 315211, China
    2 Ningbo Institute for Food Control, Ningbo 315048, China
  • Received:2020-01-21 Online:2020-08-08 Published:2020-12-11
  • Contact: XING Jiali,LI Hesheng
  • Supported by:
    Science and Technology Plan Program of State Administration for Market Regulation(2019MK080);the Basic Public Welfare Research Project of Zhejiang Province(LGC20C200013);the Modern Service Industry Project of Ningbo(2019F1017);the Natural Science Foundation of Ningbo(2019A610438);the Natural Science Foundation of Ningbo(2019A610437);the Natural Science Foundation of Ningbo(2018A610223);the Natural Science Foundation of Ningbo(2018A610336);Fan-3315 Innovation Team of Ningbo(2018B-18-C);Ningbo High-Tech Elite Innovation Team(甬高科[2018]63号)

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摘要：

当前水中酚类化合物种类不清、危害不明，多种酚类化合物的同时检测方法不成熟，因此建立水中多种酚类化合物同时检测的方法具有重要现实意义。该研究建立了固相萃取结合气相色谱-串联质谱同时检测水中18种酚类化合物的分析方法。实验选择超纯水为空白样品，采用固相萃取技术富集、提取水中的酚类化合物，同时对水样初始pH值、洗脱液的种类、洗脱液的用量等条件进行优化，从而确定出最优的前处理方法，最后利用气相色谱-串联质谱法对不同种类的酚类化合物同时进行定量检测。实验结果表明，在初始水样pH值为3.0、不衍生等条件下，使用10 mL乙酸乙酯洗脱，控制洗脱速度为1 mL/min，经固相柱富集净化，氮吹浓缩后，用气相色谱-质谱仪（EI源）测定，选择离子模式监测，外标法定量。结果表明，以3倍信噪比结合浓度外推法确定方法检出限，为0.04~0.6 μg/L；18种酚类化合物的加标回收率为51.7%~117.3%，相对标准偏差为3.1%~7.4%。应用建立的方法分别检测了河流湖泊水、生活用水、生产用水3大类6种不同的水质。检测结果表明，河流湖泊水中酚类化合物所含种类最多，含量最高。研究建立的方法不需要衍生，简化了前处理方法，操作简单，且准确性高，重复性好，可同时检测复杂水体中多种酚类化合物，能显著提高酚类化合物的分析速率。该方法的建立对我国水中酚类化合物残留水平的控制、检测标准的制定和管理措施的采取，都具有重要的理论和现实意义。

关键词: 气相色谱-串联质谱, 固相萃取, 检测, 酚类化合物, 水

Abstract:

At present, the kinds and the hazards of phenolic compounds in water were unclear. Research aimed at methods for the simultaneous detection of multiple phenolic compounds is still in its nascent stages. It is necessary to establish a method for the simultaneous determination of phenolic compounds in water. An analytical method was developed for the simultaneous determination of the 18 phenolic compounds in water by gas chromatography-tandem mass spectrometry (GC-MS/MS) coupled with solid phase extraction (SPE). The phenolic compounds in water were enriched and separated on an SPE column. The optimal pretreatment method was established by optimizing the chromatographic and mass spectrometric conditions. The effects of the initial pH of the water sample, type of eluting solvent, and dosage of the washing solution were investigated. Then, the 18 phenolic compounds in the water samples were determined. The optimal pretreatment extraction conditions were determined to be as follows:final pH of water sample, 3.0; eluting solvent, ethyl acetate (10 mL); and elution rate, 1 mL/min. The phenolic compounds enriched and purified by SPE were finally determined by GC-MS/MS with an electrospray ionization (EI) source. The phenolic compounds were then quantitatively analyzed by the external standard method. The average recoveries of the 18 phenolic compounds were in the range of 51.7%-117.3% at four spiked levels, and the relative standard deviations (RSDs) were in the range of 3.1%-7.4%. The limits of detections (LODs) were 0.04-0.6 μg/L. Good linear relationships were observed for the phenolic compounds in their corresponding concentration ranges. The developed method was applied to determine the phenolic compounds in six kinds of water samples from rivers and lakes, domestic water, and process water. Fifteen of the phenolic compounds were detected, but 4-nonylphenol, 3-methyl-4-nitrophenol, and 2-methyl-4, 6-dinitrophenol were not. Moreover, bisphenol A, 2, 4, 6-tribromophenol, and 2, 4-dibromophnol had the highest contents of 49.4 μg/L. The contents and kinds of phenolic compounds in the rivers and lakes were highest. However, the contents of phenolic compounds in the domestic water were adverse compared with the rivers and lakes, in accord with National Standard GB 8537-2008. As opposed to traditional analytical methods, the present method is characterized by simple operation without derivative or the need for anhydrous sodium sulfate for water removal, as well as high sensitivity, good stability, and reliability. The establishment of this method has important theoretical and practical significance for the development of standards and for the control of residue phenolic residue levels in water.

Key words: gas chromatography tandem mass spectrometry (GC-MS/MS), solid phase extraction (SPE), determination, phenolic compounds, water