固相萃取-气相色谱质谱法测定水中15种新型溴代阻燃剂的方法研究  

Methodology for determination of 15 novel alternative flame retardants in water by solid phase extraction and gas chromatography-mass spectrometry

作　　者：韩凤婵 胡焚 高煜东 张超 奚晔 赵宜静[2] 詹铭[2] 金志萍 郑唯韡[1] HAN Feng-chan;HU Fen;GAO Yu-dong;ZHANG Chao;XI Ye;ZHAO Yi-jing;ZHAN Ming;JIN Zhi-ping;ZHENG Wei-wei(National Health Commission Key Laboratory of Health Technology Assessment,Key Laboratory of Public Health Safety of Ministry of Education,School of Public Health,Fudan University,Shanghai 200032,China;Shanghai Pudong New Area Center for Disease Control and Prevention,Fudan University Pudong Institute of Preventive Medicine,Shanghai 200136,China;Shanghai Fengxian District Nanqiao Town Community Health Service Center,Shanghai 201499,China)

机构地区：[1]复旦大学公共卫生学院,公共卫生安全教育部重点实验室,国家卫生健康委员会卫生技术评估重点实验室,上海200032 [2]上海市浦东新区疾病预防控制中心,复旦大学预防医学研究院,上海200136 [3]上海市奉贤区南桥镇社区卫生服务中心,上海201499

出　　处：《环境与职业医学》2019年第10期942-948,共7页Journal of Environmental and Occupational Medicine

基　　金：国家自然科学基金项目（81773379,81202165）;上海市卫生计生系统优秀青年人才培养计划项目（2017YQ023）;上海市卫计委项目-奉贤区卫生科技发展基金项目（201540117）

摘　　要：[背景]传统的溴代阻燃剂多溴联苯醚因对人类及动物具有健康危害而被禁用于商业产品中。新型溴代阻燃剂(NBFRs)作为其替代物逐渐被使用。NBFRs也存在潜在的健康危害,其暴露评估不容忽视。[目的]建立水中NBFRs的固相萃取-气相色谱质谱检测方法。[方法]NBFRs单标标样分别经电子轰击离子源(EI源)和负化学离子源(NCI源)的气相色谱-质谱联用仪进行准确定性,并优化质谱参数。固相萃取条件优化过程中,以二氯甲烷和正己烷(V∶V,1∶1)混合液为洗脱液,用20 LNBFRs的加标水样经XAD-2、XAD-8、C18吸附浓缩以选择吸附剂种类;并进一步优化合适吸附剂的洗脱次数。最后,进行方法学验证并将所建立的方法应用于上海市自来水和中国北方某农村地区地下水样品分析。[结果]NCI源对NBFRs的灵敏性优于EI源,XAD-2具有较好的吸附效能,洗脱4次时样品回收率可满足大体积水样分析的质控要求。NCI源对15种NBFRs的仪器检出限(IDL)范围为0.001~1.0 ng/mL,线性范围为0.005~200 ng/mL,决定系数(R2)范围为0.995 4~0.999 9。低、中、高质量浓度NBFRs加标水样回收率范围分别为62.3%~112.2%、61.1%~112.1%、65.4%~107.0%,精密度范围分别为1.5%~20.8%、1.0%~26.1%、0.7%~11.5%。NBFRs在上海市自来水和中国北方某农村地区地下水样均有不同程度的检出。[结论]该方法基本满足大体积水样中NBFRs检测的质量控制要求,并成功用于水样分析。[Background] Traditional brominated flame retardants, polybrominated biphenyl ethers, have been prohibited from being used in commercial products because of their health hazards on human and animals. Novel brominated flame retardants(NBFRs) have gradually been used as substitution. Due to their potential health hazards, NBFRs exposure assessment cannot be ignored.[Objective] This methodological study aims to establish a method for determination of NBFRs in water by solid phase extraction and gas chromatography-mass spectrometry.[Methods] Each NBFR standard sample was separately qualitatively analyzed by gas chromatographyelectron impact ionization-mass spectrometry(GC-EI-MS) and gas chromatography-negative chemical ionization-mass spectrometry(GC-NCI-MS) to optimize parameters of mass spectrometry. In the optimization of solid phase extraction, the mixture of dichloromethane and hexane(V : V, 1 : 1) was used as elution solvents;the spiked water samples(20 L) of NBFRs were extracted using three kinds ofpacked columns, XAD-2, XAD-8, and C18, to select appropriate adsorbents. In addition, the elution times were optimized for packed columns with appropriate adsorbents. Finally, this proposed analysis protocol was validated and applied to the tap water samples collected from Shanghai and groundwater samples from a rural area in northern China.[Results] A higher sensitivity was found in identifying NBFRs by GC-NCI-MS than by GC-EI-MS. XAD-2 showed a good adsorption efficiency, and the recovery rate met the requirements for quality control of large-volume water sample analysis when the samples were eluted for four times. The instrument detection limit(IDL) of GC-NCI-MS was 0.001-1.0 ng/mL for 15 target chemicals;the linearity range was 0.005-200 ng/mL;the range of determination coefficients(R2) was 0.995 4-0.999 9. The recovery ranges of low-, mid-, high-concentration spiked water samples were 62.3%-112.2%, 61.1%-112.1%, and 65.4%-107.0%, respectively;and the relative standard deviations(RSD, n=5) were 1.5%-20.8%, 1.0%-

关 键 词：固相萃取 气质色谱-质谱联用 新型溴代阻燃剂 水样 

分 类 号：R123[医药卫生—环境卫生学]