卤化丁基橡胶塞中可提取多环芳烃的GC-MS/MS筛查法

目的： 建立卤化丁基橡胶塞中17种可提取多环芳烃的GC-MS/MS筛查方法。方法： 采用二氯甲烷-丙酮（1：1）对样品进行提取，采用GC-MS/MS法对目标多环芳烃进行检测。色谱-质谱条件：采用HP-5MS（30.0 m×0.25 mm×0.25 μm）毛细管色谱柱，柱温为程序升温（初试温度50℃，保持3 min，以25℃·min^-1升至160℃，以18℃·min^-1升至250℃，保持5 min，最后以15℃·min^-1升至300℃，保持5 min），载气为高纯氦气，柱流速1.5 mL·min^-1，进样口温度为320℃，不分流进样，进样量1.0 μL；多反应监测模式（MRM），离子源温度300℃，接口温度300℃。结果： 17种多环芳烃在检测浓度范围内线性良好（r²>0.999），检测下限为0.05~2 ng·mL^-1，3个水平加标回收率试验的平均回收率（n=9）为94.0%~118.9%，RSD为0.38%~6.9%，卤化丁基橡胶塞样品中可检出7种低分子量多环芳烃，包括萘、苊烯、苊、芴、菲、荧蒽、芘。结论： 检测方法预处理简便，灵敏度高，专属性好，适用于卤化丁基橡胶塞中可提取多环芳烃的筛查。

Objective: To establish a GC-MS/MS method for screening of 17 kinds of polycyclic aromatic hydrocarbons(PAHs) in halogenated butyl rubber stoppers. Methods: The samples were extracted by dichloromethane-acetone(1:1)hybrid solvents,and the target PAHs were determined using GC-MS/MS. GC-MS conditions:an HP-5MS capillary column(30 m×0.25 mm×0.25 μm) was adopted with helium (1.5 mL·min^-1) used as the carrying gas;the column temperature was programmed to start at 50℃ for 3 min,and raised at a rate of 25℃·min^-1 to 160℃,then raised to 250℃ at a rate of 18℃·min^-1 and held for 5 min,and was finally raised to 300℃ at a rate of 15℃·min^-1 and held for 5 min;the inlet temperature was 320℃, the injection volume was 1 μL with splitless injection model. Quantitative analysis was carried out by triple quadrupole mass spectrometer with MRM model;the source temperature was 300℃ and the transmission line temperature was 300℃. Results: 17 kinds of PAH had good linearity(r²>0.999) in the tested concentration ranges,and the limits of detection ranged from 0.05 ng·mL^-1 to 2.0 ng·mL^-1. The average recovery rates(n=9) ranged from 94.0% to 118.9% at three spiked levels,with RSD of 0.38%-6.9%. Seven kinds of low-molecular-mass PAH including naphthalene,acenaphthylene,acenaphthene,fluorene,phenanthrene,fluoranthene,and pyrene were detected in halogenated butyl rubber stoppers. Conclusion: This sensitive and specific method with simple pretreatment procedures is suitable for screening of PAHs in halogenated butyl rubber stoppers.

[1] SMITH EJ,NASH RJ.Elastomeric closures for parenterals[M]//AVIS KE,LIEBERMAN HA,LACHMAN L.Pharmaceutical Dosage Forms:Parenteral Medications.Volume 1.2nd Ed.New York:Marcel Dekker Inc.,1992:445
[2] MA JP,XIAO RH,LI JH,et al.Determination of 16 polycyclic aromatic hydrocarbons in environmental water samples by solid-phase extraction using multi-walled carbon nanotubes as adsorbent coupled with gas chromatography-mass spectrometry[J].J Chromatogr A,2010,1217(34):5462
[3] PURCARO G,MORET S,BU?AR MM,et al.Ultra-high performance liquid chromatographic method for the determination of polycyclic aromatic hydrocarbons in a passive environmental sampler[J].J Sep Sci,2012,35(8):922
[4] International Carbon Black Association.Carbon Black User's Guide,Safety,Health,& Environmental Information[S].2004
[5] MORET S,CONTE LS.Off-line LC-LC determination of PAHs in edible oils and lipidic extracts[J].J High Resolut Chromatogr,1998,21(4):253
[6] REHWAGEN M,MüLLER A,MASSOLO L,et al.Polycyclic aromatic hydrocarbons associated with particles in ambient air from urban and industrial areas[J].Scie Total Environ,2005,348(1-3):199
[7] DEBAJYOTI G,SHREYA G,DUTTA TK,et al.Current state of knowledge in microbial degradation of polycyclic aromatic hydrocarbons(PAHs):a review[J].Front Microbiol,2016,7:1369
[8] IARC.Diesel and gasoline engine exhausts and some nitroarenes[J].IARC Monogr Eval Carcinog Risks Hum,1989,46:1
[9] KEITH LH,TELLIARD WA.Priority pollutants.Ⅰ.A perspective view[J].Environ Sci Technol,1979,13(4):416
[10] Commission Regulation(EU) No 1272/2013 of 6 December 2013:amending Annex ⅩⅦ to Regulation(EC) No 1907/2006 of the European Parliament and of the Council on the Registration,Evaluation,Authorisation and Restriction of Chemicals(REACH) as regards polycyclic aromatic hydrocarbons[S].2013
[11] 谢忠麟.多环芳烃与橡胶制品[J].橡胶工业,2011,58(6):359 XIE ZL.Polycyclic aromatic hydrocarbons(PAHs)in rubber products[J].China Rubber Ind,2011,58(6):359
[12] NORWOOD DL,PRIME D,DOWNEY BP,et al.Analysis of polycyclic aromatic hydrocarbons in metered dose inhaler drug formulations by isotope dilution gas chromatography/mass spectrometry[J].J Pharm Biomed Anal,1995,13(3):293
[13] 化学药品与弹性体密封件相容性研究技术指导原则(试行)[S].2018 Technologic Guidelines for the Research on the Compatibility of Chemical Drugs with Elastomeric Closures(Provisional)[S].2018
[14] SERPE FP,ESPOSITO M,GALLO P,et al.Optimisation and validation of an HPLC method for determination of polycyclic aromatic hydrocarbons(PAHs) in mussels[J].Food Chem,2010,122(3):920
[15] YUAN X,JIANG Y,YANG CX,et al.Determination of 16 kinds of polycyclic aromatic hydrocarbons in atmospheric fine particles by accelerated solvent extraction coupled with high performance liquid chromatography[J].Chin J Anal Chem,2017,45(11):1641
[16] 戴雪伟,卫碧文,望秀丽,等.超高效合相色谱快速分析塑料制品中的18种多环芳烃[J].色谱,2015,33(10):1059 DAI XW,WEI BW,WANG XL,et al.Determination of 18 polycyclic aromatic hydrocarbons in plastic products by ultra performance convergence chromatography[J].Chin J Chromatogr,2015,33(10):1059
[17] RASCóN AJ,AZZOUZ A,BALLESTEROS E.Trace level determination of polycyclic aromatic hydrocarbons in raw and processed meat and fish products from European markets by GC-MS[J].Food Control,2019,101:198
[18] LI YJ,ZHU JP.Identification of sink spots in two thermal desorption GC/MS systems for the analysis of polycyclic aromatic hydrocarbons[J].Anal Chim Acta,2017,961:67
[19] MA TT,SHEN XF,YANG C,et al.Covalent immobilization of covalent organic framework on stainless steel wire for solid-phase microextraction GC-MS/MS determination of sixteen polycyclic aromatic hydrocarbons in grilled meat samples[J].Talanta,2019,201:413
[20] HALEYUR N,SHAHSAVARI E,MANSUR AA,et al.Comparison of rapid solvent extraction systems for the GC-MS/MS characterization of polycyclic aromatic hydrocarbons in aged,contaminated soil[J].MethodsX,2016,3:364
[21] 李志艳,梅蕾,张毅兰.气质联用法测定药用橡胶中挥发性潜在迁移物[J].中国医药工业杂志,2017,48(3):413 LI ZY,MEI L,ZHANG YL.Determination of volatile potential migrants in rubber for pharmaceutical use by GC-MS[J].Chin J Pharm,2017,48(3):413
[22] ACHTEN C,ANDERSSON JT.Overview of polycyclic aromatic compounds(PAC)[J].Polycycl Aromat Compd,2015,35(2-4):177
[23] LAWAL AT.Polycyclic aromatic hydrocarbons:a review[J].Cogent Environ Sci,2017,3(1):1
[24] EPA.Integrated Risk Information System(IRIS)[DB/OL].[2020-02-09].https://www.epa.gov/iris