超声辅助萃取-凝胶渗透色谱净化结合超高效液相色谱-高分辨质谱检测食用鱼肉中12种卤代有机污染物  

Determination of 12 halogenated organic pollutants in edible fish by ultra performance liquid chromatography-high resolution mass spectrometry combined with ultrasound-assisted extraction and gel permeation chromatography purification

作　　者：祝亦哲 郑锐芬 樊子昊 刘灵 叶靖瑶 王凯 唐才明 ZHU Yizhe;ZHENG Ruifen;FAN Zihao;LIU Ling;YE Jingyao;WANG Kai;TANG Caiming(Research Center for Eco-Environmental Engineering,Dongguan University of Technology,Dongguan 523808,China;Guangdong Key Laboratory of Environmental Resources Utilization and Protection,Guangzhou Institute of Geochemistry,Chinese Academy of Sciences,Guangzhou 510640,China)

机构地区：[1]东莞理工学院生态环境工程技术研发中心,广东东莞523808 [2]中国科学院广州地球化学研究所,广东省环境资源利用与保护重点实验室,广东广州510640

出　　处：《色谱》2025年第1期68-77,共10页Chinese Journal of Chromatography

基　　金：广东省基础与应用基础研究基金项目(2021B1515140019,2022A1515140049);广东省教育厅科研项目(2018WQNCX307);国家自然科学基金项目(U23A2056);广东省省级科技计划项目(2023B1212060049)。

摘　　要：卤代有机污染物(HOPs)因具有持久性、生物积累性、毒性等而广受关注。本研究应用超声辅助萃取和凝胶渗透色谱净化结合超高效液相色谱-高分辨质谱,建立了同时检测常见食用鱼肉中12种HOPs的方法。根据HOPs特性和鱼肉样品特点选择高效、可靠的前处理方法,优化了萃取净化方法和色谱-质谱参数。鱼肉通过甲醇-乙腈(1∶1,v/v)混合溶剂提取,低温高速离心,上清液经氮吹浓缩后转溶于乙酸乙酯-环己烷(1∶1,v/v)混合溶剂,过滤后由凝胶渗透色谱净化,洗脱液经氮吹浓缩后复溶,进样分析。液相色谱流动相为含2 mmol/L乙酸铵的水溶液和乙腈,通过梯度洗脱,离子源为电喷雾电离源,负离子模式,质谱数据采集方式为全扫描和数据依赖采集,同位素内标法定量。结果显示,12种HOPs均具有良好的线性关系,定量限为0.5 ng/g。以混合鱼肉为基质,在4、40和400 ng/g加标水平下,12种HOPs的加标回收率为67.6%~133.8%,RSD为0.5%~15.6%。应用本方法对27份实际鱼肉样品进行检测,发现鱼肉中均含有HOPs,含量为未检出~4.52 ng/g。该方法灵敏度好,准确度高,可作为鱼肉中HOPs的高通量筛查和定量检测方法。Halogenated organic pollutants(HOPs)have attracted considerable attention owing to their persistence,bioaccumulation,and toxicity.The development of methods to detect HOPs in fish is challenging owing to the compositional complexity of fish matrices,which contain high levels of lipids and relatively low concentrations of HOPs.In addition,the lipophilicity of most HOPs renders their extraction difficult.Moreover,the simultaneous determination of multiple HOPs to achieve the high-throughput screening of these analytes is complex.In this study,a reliable and efficient pretreatment method based on ultrasound-assisted extraction,gel permeation chromatography purification,and ultra performance liquid chromatography-high resolution mass spectrometry(UPLC-HRMS)was developed for the determination of 12 HOPs in edible fish.The procedures of sample extraction and purification and LC-HRMS detection parameters were optimized to improve the performance of the method.Fresh fish samples were thoroughly rinsed with water,and non-edible parts,including the skin,bones,and phosphorus,were removed.The fish were weighed,cut into small pieces,and vacuum freeze-dried for 48 h.Subsequently,a freeze grinder was used to grind the dried fish into a fine powder.Exactly 2 g of the fish powder was weighed,fortified with isotope-labeled internal standards of the HOPs,and allowed to stand for 5 min.Methanol-acetonitrile(1∶1,v/v)was then added,followed by vortex mixing and ultrasonication.After centrifugation,the supernatant was transferred to a fresh tube.The extraction process was repeated twice and all extracts were combined.The extract was evaporated under a gentle nitrogen flow and redissolved in a mixture of ethyl acetate-cyclohexane(1∶1,v/v).The sample mixture was cleaned using gel permeation chromatography,and the eluate was collected and concentrated under a nitrogen flow.Sample residuals were reconstituted with water-methanol(1∶1,v/v)prior to instrumental analysis.Chromatographic separation was performed using an ACQUITY UPLC BEH

关 键 词：凝胶渗透色谱 超高效液相色谱-高分辨质谱 卤代有机污染物 食用鱼肉 

分 类 号：O658[理学—分析化学]