色谱

色谱 ›› 2025, Vol. 43 ›› Issue (8): 950-958.DOI: 10.3724/SP.J.1123.2025.01030

• 研究论文 • 上一篇    下一篇

超声辅助气液微萃取-气相色谱-质谱法测定海带中16种多环芳烃

牟志国1, 王译旋1, 郭炎琳1, 金香子1, 李东浩1,*(), 赵锦花1,2,*()   

  1. 1.延边大学理学院化学系，农产品质量与安全评价吉林省高校重点实验室，吉林 延吉 133002
    2.延边大学分析测试中心，吉林 延吉 133002
  • 收稿日期:2025-02-10 出版日期:2025-08-08 发布日期:2025-07-28
  • 通讯作者: Tel：（0433）2436458，E-mail：zhaojinhua@ybu.edu.cn（赵锦花）；Tel：（0433）2436456，E-mail：dhli@ybu.edu.cn（李东浩）.
  • 基金资助:
    国家自然科学基金项目(22206171);国家自然科学基金项目(22176164);吉林省科技发展计划项目(YDZJ202501ZYTS410)

Determination of 16 polycyclic aromatic hydrocarbons in seaweed by ultrasound-assisted gas-liquid microextraction coupled with gas chromatography-mass spectrometry

MU Zhiguo1, WANG Yixuan1, GUO Yanlin1, JIN Xiangzi1, LI Donghao1,*(), ZHAO Jinhua1,2,*()   

  1. 1. Department of Chemistry，College of Science，Yanbian University，Key Laboratory of Agrifood Quality and Safety Evaluation of Jilin Province，Yanji 133002，China
    2. Analysis and Inspection Center，Yanbian University，Yanji 133002，China
  • Received:2025-02-10 Online:2025-08-08 Published:2025-07-28
  • Supported by:
    National Natural Science Foundation of China(22206171);National Natural Science Foundation of China(22176164);Jilin Foundation for Program of Science and Technology Research(YDZJ202501ZYTS410)

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摘要：

基于超声辅助气液微萃取（UA-GLME）联用气相色谱-质谱（GC-MS）技术，建立了测定海带中16种多环芳烃（PAHs）的检测方法，并对样品前处理和色谱条件进行了优化。海带样品用二氯甲烷-正己烷（1∶1，v/v）混合溶剂超声辅助提取后，经过气液微萃取技术进一步萃取，采用DB-5MS毛细管柱（30 m×0.25 mm×0.25 µm）分离，使用全扫描（SCAN）、选择离子监测（SIM）模式进行检测分析。结果表明，本方法在最优的条件下，PAHs在5.0~2 000 ng/mL范围内具有良好的线性关系，相关系数（R2）均大于0.999，仪器检出限（LOD）和方法检出限（MDL）分别为0.001~0.01 μg/mL和0.004~0.04 mg/kg。16种PAHs在高、中、低3个水平下的加标回收率为62.32%~91.64%，RSD为2.94%~9.15%。本方法显著减少了脂溶性和共萃取物的干扰，其中长链烷烃、脂肪酸及甾醇类等主要共萃取物的去除率大幅提升。SIM模式下色谱图的比较分析结果表明，UA-GLME方法显著优化了PAHs的峰形，有效提高了信噪比和定量分析的准确性，同时展现出对海带基质中复杂干扰物的显著抗干扰能力。采用所建立的方法对东海、渤海、黄海及南海海带样品进行分析测定，结果显示16种PAHs均有不同程度的检出。该方法简化了复杂的样品前处理过程，并适用于海带中PAHs的定性、定量分析，为海洋环境污染和风险评价提供了可靠的技术支持。本方法可通过优化超声条件与溶剂体系，拓宽在其他复杂基质样品中的适用性，为环境监测与污染物溯源提供新策略。

关键词: 超声辅助, 气液微萃取, 气相色谱-质谱法, 多环芳烃, 海带

Abstract:

The increasing demand for the detection of polycyclic aromatic hydrocarbons（PAHs） in the complex matrices of the marine environment requires overcoming the limitations of traditional detection methods， particularly in terms of sensitivity and accuracy. Analyzing PAHs in seaweed matrices is often hindered by significant interference owing to the complex compositions of these matrices， which compromises both qualitative identification and quantitative determination. To address these challenges， this study developed an innovative and efficient method for detecting PAHs based on ultrasound-assisted gas-liquid microextraction（UA-GLME） coupled with gas chromatography-mass spectrometry（GC-MS）. The developed method involves extracting a seaweed sample with dichloromethane-hexane（DCM-HEX）（1∶1， v/v）， followed by further GLME. The separated sample is then analyzed using a DB-5MS capillary column（30 m×0.25 mm×0.25 µm） in SCAN and selective ion monitoring（SIM） modes. PAH extraction efficiencies were enhanced while significantly minimizing the co-extraction of interfering compounds by exploiting the cavitation effects of ultrasound. This optimization procedure improves both PAH-detection sensitivity and accuracy while reducing matrix effects. Under optimal conditions， the PAHs showed excellent linearity in the range of 5.0-2 000 ng/mL， with correlation coefficients（R2） exceeding 0.999. Limits of detection（LODs） ranged between 0.001 and 0.01 μg/mL， while method detection limits（MDLs） of 0.004–0.04 mg/kg were recorded. The recovery rates at high， medium， and low concentration levels were 62.32%-91.64%， with relative standard deviations（RSDs） between 2.94% and 9.15%. The developed method significantly reduces interference from lipophilic and low-volatility co-extractives， while removing co-extractives， such as long-chain alkanes， fatty acids， and sterols， at rates of up to 100%. Chromatographic comparisons revealed that the UA-GLME method delivers superior peak shapes for the target PAHs， enhanced signal-to-noise ratios， high quantitative accuracies， and remarkable resistance to seaweed-matrix interference. The method was used to detect PAHs in seaweed samples from the East China Sea， Bohai Sea， Yellow Sea， and South China Sea， with the 16 PAHs detected at varying levels. Both low-molecular-weight PAHs（such as naphthalene， phenanthrene， and fluorene） and high-molecular-weight PAHs（such as benzo［a］pyrene and benzo［k］fluoranthene） were detected at high rates. This method offers a reliable approach for the qualitative and quantitative analysis of PAHs in seaweed， thereby providing valuable technical support for assessing marine environmental pollution and evaluating risks. The developed method can be extended to other complex matrices by optimizing the ultrasound conditions and solvent system， thereby offering new strategies for environmental monitoring and pollutant-source tracing.

Key words: ultrasound-assisted（UA）, gas-liquid microextraction（GLME）, gas chromatography-mass spectrometry（GC-MS）, polycyclic aromatic hydrocarbons（PAHs）, seaweed

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