固相萃取-气相色谱-静电场轨道阱高分辨质谱测定海水中4类34种含氯持久性有机污染物  

Determination of four classes of 34 chlorinated persistent organic pollutants in seawater by solid-phase extraction and gas chromatography-electrostatic field orbitrap high resolution mass spectrometry

作　　者：高梦浩 栗笑迎 高媛[2] 张海军[2] 陈吉平[2] GAO Menghao;LI Xiaoying;GAO Yuan;ZHANG Haijun;CHEN Jiping(College of Environmental Sciences and Engineering,Dalian Maritime University,Dalian 116026,China;Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China)

机构地区：[1]大连海事大学环境科学与工程学院,辽宁大连116026 [2]中国科学院大连化学物理研究所,辽宁大连1160230

出　　处：《色谱》2025年第4期345-354,共10页Chinese Journal of Chromatography

基　　金：国家重点研发计划(2022YFC3105500);国家自然科学基金(22276186).

摘　　要：海洋在新污染物的环境迁移、转化过程中起到重要作用。海水中新污染物的准确定量是厘清其环境行为、评估其环境风险的基础。本研究采用液液萃取和固相萃取建立海水样品前处理方法,基于气相色谱-静电场轨道阱高分辨质谱(GC-Orbitrap-HRMS)测定海水中4类34种含氯持久性有机污染物(POPs)的定量分析方法,即:25种有机氯农药(OCPs)、6种多氯联苯(PCBs)同系物、短链氯化石蜡(SCCPs)和2种德克隆(DPs)同分异构体。通过优化液液萃取提取溶剂种类,选择二氯甲烷进行萃取。随之对固相萃取不同洗脱溶剂进行评价,最终使用体积比为9∶1的正己烷和丙酮混合溶剂进行洗脱。质谱采用电子轰击源(EI)(正离子模式)监测OCPs和PCBs目标化合物离子,采用负化学源(NCI)监测SCCPs和DPs,内标法定量。结果表明,所建立的方法具有较低的检出限,34种含氯POPs检出限为0.006~2.78 ng/L,定量限为0.02~11.12 ng/L;方法准确度和精密度通过测定目标化合物的加标回收率得到验证,低、中、高3个加标水平下的回收率为70.6%~128.9%,相对标准偏差(n=6)为0.2%~19.2%。通过实际海水样品分析显示,SCCPs的检出率和浓度水平最高,质量浓度最高为130.6 ng/L,需要持续重点关注。该方法前处理操作简便,灵敏度高,样品需求量少,适用于大批量海水样本中多种含氯POPs的痕量检测。Ocean acts as a“sink”for pollutants in the natural environment.Consequently,issues focused on marine pollution from terrestrial origin is attracting increasing attention.Persistent organic pollutants(POPs),including organochlorine pesticides(OCPs),polychlorinated biphenyls(PCBs),short-chain chlorinated paraffins(SCCPs),and dechlorane plus isomers(DPs),are serious hazards for both the environment and humans.These POPs have been widely detected in the marine environment and are typically present at trace levels;however,separating and determining individual contaminants require large amounts of sampling and time.Establishing an accurate analytical method for determining typical POPs is critical for studying their environmental behavior and associated ecological risks to the marine environment.In this study,we developed a method based on solid-phase extraction(SPE)combined with gas chromatography-electrostatic field orbitrap high resolution mass spectrometry(GC-Orbitrap-HRMS)for determining 34 chlorinated POPs in seawater,including 25 OCPs,six PCB congeners,SCCPs and two DPs.The chromatographic conditions and MS parameters were optimized,and the effects of the extraction solvent and purification method were systematically studied.Dichloromethane exhibited satisfactory extraction efficiencies during the liquid-liquid extraction(LLE)of seawater samples,with recoveries of 73.1%-120.5%for OCPs,87.2%-101.7%for PCBs,105.5%for SCCPs,and 74.9%-78.6%for DPs,respectively.Purification using a SPE column with 500 mg of Florisil was adopted,and 9∶1(v/v)n-hexane/acetone was confirmed as the eluent with recoveries between 68.2%and 122.8%for all the 34 chlorinated POPs.A DB-5MS(15 m×0.25 mm×0.10μm)capillary chromatographic column was used to separate the target compounds,with an electron ionization(EI)source used to detect OCPs and PCBs,whereas SCCPs and DPs were determined in negative chemical ionization(NCI)source.All target compounds were analyzed in full-scan mode.An internal standard quantification method was used for

关 键 词：固相萃取 气相色谱-静电场轨道阱高分辨质谱 含氯持久性有机污染物 海水 

分 类 号：O658[理学—分析化学]