QuEChERS结合超高效液相色谱-四极杆/静电场轨道阱高分辨质谱法测定PM_(2.5)中氯化石蜡含量  

Determination of chlorinated paraffins in PM_(2.5)by QuEChERS combined with ultra-high performance liquid chromatography-quadrupole/orbitrap high resolution mass spectrometry

作　　者：闫文彦 王超[2] 刘娟 孙轶斌 顾雯[2] 陆一夫[2] 方珂 万祎[3] 唐宋 YAN Wenyan;WANG Chao;LIU Juan;SUN Yibin;GU Wen;LU Yifu;FANG Ke;WAN Yi;TANG Song(Center for Global Health,School of Public Health,Nanjing Medical University,Nanjing,Jiangsu 211166,China;China CDC Key Laboratory of Environment and Population Health/National Institute of Environmental Health,Chinese Center for Disease Control and Prevention,Beijing 100021,China;College of Urban and Environmental Sciences,Peking University,Beijing 100871,China)

机构地区：[1]南京医科大学公共卫生学院全球健康中心,江苏南京211166 [2]中国疾病预防控制中心环境与人群健康重点实验室/中国疾病预防控制中心环境与健康相关产品安全所,北京100021 [3]北京大学城市与环境学院,北京100871

出　　处：《环境与职业医学》2024年第10期1087-1094,1108,共9页Journal of Environmental and Occupational Medicine

基　　金：国家自然科学基金面上项目(82273677);国家自然科学基金双碳专项项目(82241091);北京市自然科学基金项目:(7244456)。

摘　　要：[背景]既往空气细颗粒物(PM_(2.5))中氯化石蜡(CPs)的研究多集中在短链及中链(SCCPs、MCCPs),少有研究同时定量检测其中的短、中、长链氯化石蜡(LCCPs)。建立一种同时提取并测定PM_(2.5)中SCCPs、MCCPs、LCCPs的方法可为其环境监测和人类健康风险评估提供技术支持。[目的]QUEChERS前处理方法结合超高效液相色谱串联四极杆/静电场轨道阱高分辨质谱,建立同时测定PM_(2.5)中SCCPs、MCCPs、LCCPs的方法。[方法]优化QuEChERS方法的提取溶剂、提取盐和提取步骤,依次比较4种提取溶剂[乙腈、二氯甲烷和正己烷溶剂依次提取;乙腈∶二氯甲烷∶正己烷=1∶1∶2(v/v/v)混合溶剂;1%乙酸-乙腈∶二氯甲烷∶正己烷=1∶1∶1(v/v/v)混合溶剂;乙腈∶二氯甲烷∶正己烷=1∶1∶1(v/v/v)混合溶剂]、2种除水盐(无水MgSO4+NaCl和无水Na2SO4+NaCl)、2种净化盐(C18和PSA)和4种涡旋时间(5、7.5、10、12.5 min)条件下目标物质的提取效率。采用内标法对样品进行定量分析,并对优化后的QuEChERS方法进行线性范围、检出限等方法学指标的评估。[结果]SCCPs、MCCPs、LCCPs在10~1000 ng·mL^(−1)范围内线性关系良好,相关系数(R2)均大于0.96。方法检出限(MDLs)为0.01~0.29 ng·m^(-3)。SCCPs、MCCPs、LCCPs在低、中、高三个浓度的加标回收率范围分别为77.38%~81.64%、93.11%~99.78%、87.41%~101.39%,相对标准偏差(RSD)为2.90%~12.84%。采用本方法对石家庄11个PM_(2.5)样品中的CPs水平进行了测定,ΣSCCPs、ΣMCCPs和ΣLCCPs检出率均为100%,质量浓度范围分别为0.24~2.18 ng·m^(-3)(均值为0.84 ng·m^(-3))、0.17~1.67 ng·m^(-3)(均值为0.70 ng·m^(-3))和0.01~0.16 ng·m^(-3)(均值为0.04 ng·m^(-3)),在ΣCPs中的占比分别为52.95%、44.39%和2.66%。[结论]本研究所建立的方法操作简便、耗时短、溶剂消耗少,且可同时检测PM_(2.5)中SCCPs、MCCPs、LCCPs,适用于PM_(2.5)样品大批量测定,也可为PM_(2.5)中其他卤代有机物�[Background]Previous research on chlorinated paraffins(CPs)in fine particulate matter(PM_(2.5))has predominantly focused on short-and medium-chain chlorinated paraffins(SCCPs and MCCPs),and few studies could simultaneously determine short-,medium-,and long-chain chlorinated paraffins(LCCPs).Simultaneous extraction and determination of SCCPs,MCCPs,and LCCPs in PM_(2.5)could provide technical support for their environmental monitoring and human health risk assessment.[Objective]To establish a method based on QUEChERS pretreatment method in conjunction with ultra-performance liquid chromatography-quadrupole/orbitrap high resolution mass spectrometry for simultaneously determining the levels of SCCPs,MCCPs,and LCCPs in PM_(2.5).[Methods]The extraction solvents,extraction salts,and extraction steps of a QuEChERS method were optimized.The extraction efficiencies of the target substances were compared under 4 extraction solvents[acetonitrile,dichloromethane,and n-hexane solvents in sequence;acetonitrile:dichloromethane:n-hexane=1:1:2(v/v/v)mixed solvent;1%acetic acid-acetonitrile:dichloromethane:n-hexane=1:1:1(v/v/v)mixed solvent;acetonitrile:dichloromethane:n-hexane=1:1:1(v/v/v)mixed solvent],2 dehydrated salts(anhydrous MgSO4+NaCl and anhydrous Na2SO4+NaCl),2 purification salts(C18 and PSA),and 4 vortex time(5,7.5,10,and 12.5 min)conditions.Then internal standard was utilized to estimate linear range and detection limit of the refined QuEChERS approach.[Results]The linearities of SCCPs,MCCPs,and LCCPs were good in the range of 10~1000 ng·mL^(−1)with the correlation coefficients all greater than 0.96.The method detection limits(MDLs)ranged from 0.01 to 0.29 ng·m^(−3).The spiked recoveries of SCCPs,MCCPs,and LCCPs at the low,medium,and high concentrations were 77.38%-81.64%,93.11%-99.78%,and 87.41%-101.39%,respectively,and the relative standard deviations(RSDs)were 2.90%-12.84%.This method was used to determine the CPs levels in 11 PM_(2.5)samples from Shijiazhuang.The positive rates ofΣSCCPs,ΣMCCPs,andΣLCCPs w

关 键 词：氯化石蜡 细颗粒物 快速、简单、廉价、有效、坚固且安全 超高效液相色谱 四极杆/静电场轨道阱高分辨质谱 

分 类 号：R12[医药卫生—环境卫生学]