色谱

色谱

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QuEChERS结合超高效液相色谱-串联质谱同时测定螺贝类软体动物中抗生素和精神活性物质

顾骁嵘1,2, 符杰3,*, 林锋4, 伍雅婧3, 杨丹3, 陈林海3, 张爱茜1,2,3, 傅建捷1,2,3,*   

  1. 1.中国科学院生态环境研究中心环境化学与环境毒理全国重点实验室,北京 100085;
    2.中国科学院大学资源与环境学院,北京 100049;
    3.国科大杭州高等研究院环境学院全省新污染物环境与健康重点实验室,浙江 杭州 310024;
    4.浙江省淡水水产研究所农业农村部淡水健康养殖重点实验室,浙江 湖州 313001
  • 收稿日期:2026-02-12
  • 通讯作者: *Tel:8610-62849339, E-mail: jjfu@rcees.ac.cn（傅建捷）;Tel：0571-86085087,E-mail: jiefu@ucas.ac.cn（符杰）.
  • 基金资助:
    国家自然科学基金青年基金(22306040); 中国博士后科学基金面上项目(2023M744123); 国科大杭州高等研究院专项资金(2023HIAS-Y019); 中央引导地方科技发展资金项目(No.2025ZY01044); 农业农村部淡水渔业健康养殖重点实验室开放课题(ZJK202516).

Simultaneous determination of antibiotics and psychoactive substances in mollusks by QuEChERS and ultra-high performance liquid chromatography-tandem mass spectrometry

GU Xiaorong1,2, FU Jie3,*, LIN Feng4, WU Yajin3, YANG Dan3, CHEN Linhai3, ZHANG Aiqian1,2,3, FU Jianjie1,2,3,*   

  1. 1. State Key Laboratory of Environmental Chemistry and Toxicology, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China;
    2. College of Resources and Environment, University of Chinese Academy of Sciences, Beijing 100049, China;
    3. Zhejiang Key Laboratory of Environment and Health of New Pollutants, School of Environment, Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences, Hangzhou 310024, China;
    4. Key Laboratory of Healthy Freshwater Aquaculture, Ministry of Agriculture and Rural Affairs, Zhejiang Institute of Freshwater Fisheries, Huzhou 313001, China
  • Received:2026-02-12
  • Supported by:
    Youth Fund of the National Natural Science Foundation of China (No. 22306040); China Postdoctoral Science Foundation (No. 2023M744123); the Research Funds of the Hangzhou Institute for Advanced Study, University of Chinese Academy of Sciences (No. 2023HIAS-Y019); the Central Guiding Local Science and Technology Development Fund Projects (No. 2025ZY01044); Research Project of Key Laboratory of Healthy Freshwater Aquaculture, Ministry of Agriculture and Rural Affairs (No. ZJK202516).

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摘要： 抗生素(antibiotics)和精神活性物质(psychoactive substances,PSs)在水产品中的广泛检出引起高度关注,但目前缺乏关于两类物质同时高灵敏检测的分析方法。本研究开发了一种QuEChERS结合超高效液相色谱-串联质谱同时检测螺贝类中28种抗生素及10种PSs的分析方法。样品经含0.1%氨水的甲醇-乙腈溶液(1:1,V/V)提取,混合吸附剂净化后,在正离子选择反应监测(SRM)模式下检测。结果表明：化合物在0.1~50 μg/L范围内具有良好线性关系(r2>0.995),方法报告限(MRL)为0.5~2.9 ng/g。化合物在低、中、高3个加标水平(0.5、2.5、10 ng/g)下的平均回收率为70.7%~124.9%,相对标准偏差(RSD,n=6)为1.0%~18.6%。应用该法检测10份螺贝样品,检出15种抗生素和9种PSs,总和含量为未检出(nd)~4β909.2 ng/g dw(干重)。该方法灵敏高效,回收率良好,重复性稳定,适用于螺贝类软体动物中抗生素和PSs的同步快速测定。

关键词: 螺贝类软体动物, 抗生素, 精神活性物质, QuEChERS, 超高效液相色谱-串联质谱

Abstract: The widespread detection of antibiotics and psychoactive substances (PSs) in aquatic products has raised significant concerns. However, sensitive methods for detecting both compound classes simultaneously are lacking. To address this analytical gap, this study developed a novel analytical method for the determination of mollusks by QuEChERS-ultra-high performance liquid chromatography- triple quadrupole mass spectrometry (UHPLC-MS/MS). This method simultaneously determines 28 antibiotics and 10 PSs in shellfish and gastropods. During the extraction phase, target compounds were extracted using methanol-acetonitrile (1:1, V/V) containing 0.1% ammonia solution. This optimized solvent system ensured high extraction efficiency while significantly reducing matrix effects. The subsequent purification step was performed with a mixed sorbent (C18 100 mg, PSA 100 mg, GCB 100 mg, anhydrous MgSO4 300 mg). This specific combination effectively removed lipids, proteins, and pigment interferences from the sample extracts. Mass spectrometry was performed in positive electrospray ionization (ESI+) mode, with selected reaction monitoring (SRM) as the acquisition mode. Results demonstrated that all target compounds exhibited good linearity in the range of 0.1‒50 μg/L, with correlation coefficients (r2) exceeding 0.995. The instrument limits of detection (LODs) ranged from 0.002 to 0.1 ng/g, and the limits of quantification (LOQs) were between 0.005 and 0.3 ng/g. The method reporting limits (MRLs) varied from 0.5 to 2.9 ng/g. Accuracy and precision were comprehensively evaluated at three distinct spiked levels (0.5, 2.5, and 10 ng/g). The average recoveries for the targeted analytes ranged from 70.7% to 124.9%, with relative standard deviations (RSDs, n = 6) of 1.0%‒18.6%. Furthermore, the intra-day and inter-day precision values were 1.4%‒14.7% and 0.7%‒12.4%, respectively, indicating high method stability and reproducibility. The optimized method was applied to analyze antibiotics and PSs in 7 shellfish and 3 gastropod samples collected from coastal markets in Zhejiang Province, revealing the presence of 15 antibiotics and 9 PSs. Total antibiotic concentrations ranged from not detected (nd) to 3β251.3 ng/g dw(dry weight). The mean antibiotic content was 325.1 ng/g dw. Notably, sulfamethoxypyridazine emerged as the predominant antibiotic residue, presenting an average concentration of 111.7 ng/g dw and accounting for 34.5% of the total antibiotic load. The total concentrations of PSs ranged from nd to 4β909.2 ng/g dw. The mean PSs content was 490.9 ng/g dw. Ketamine was identified as the primary psychoactive contaminant, with a mean concentration of 199.2 ng/g dw, representing 40.5% of the total PSs load. In conclusion, this method is sensitive and efficient, provides satisfactory recovery and reproducibility, and is suitable for the simultaneous rapid determination of trace levels of antibiotics and PSs in shellfish and gastropod mollusks.

Key words: shellfish and gastropods mollusks, antibiotics, psychoactive substances, QuEChERS, ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS)

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