热脱附-GC/MS快速测定大气细颗粒物中支链烷烃和烷基环己烷
Determination of Branched Alkane and Alkylcyclohexane in Atmospheric Fine Particulate Matter Using Rapid Direct Thermal Desorption-GC/MS
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摘要: 建立了直接进样-热脱附-GC/MS法快速测定大气细颗粒物中7种支链烷烃和烷基环己烷类有机示踪物。为提高方法的选择性和灵敏度等指标，优化了脱附温度和时间、冷阱填料和捕集温度。采用了高、低浓度工作曲线，线性范围分别为0.25~50 ng和0.025~0.5 ng，相关系数均在0.990以上，空白加标回收率在86.2%~110%之间，实际样品加标回收率在97.1%~113%之间。当采样体积为24 m3时，各目标化合物的检出限在0.004~0.020 ng/m3之间，低于加速溶剂萃取法的检出限。利用本方法测定了北京城区采暖季和非采暖季PM2.5的实际样品，结果表明，在采暖季和非采暖季样品中，各目标物均有检出，支链烷烃含量比烷基环己烷类化合物高2个数量级，采暖季的支链烷烃和烷基环己烷类化合物的含量均明显高于非采暖季。本方法无需复杂的前处理和有机溶剂，操作简便快捷，在颗粒物中非极性化合物的快速检测方面具有很大的应用价值。
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关键词:
- 热脱附-气相色谱-质谱法 /
- 细颗粒物（PM2.5） /
- 支链烷烃 /
- 烷基环己烷 /
- 有机示踪物
Abstract: The organic molecular tracers such as branched alkane and alkylcyclohexane in PM2.5 were determined using direct thermal desorption-gas chromatography-mass spectrometry （GC/MS）. In order to improve selectivity and sensitivity of method, various parameters such as desorption temperature, desorption time, cooling trap packing, and cooling temperature were studied. Results showed that the correlation coefficients of organic molecular tracers in the range of 0.25-50 ng and 0.025-0.5 ng are all above 0.990. The recoveries of the target compounds in blank quartz filters and actual particulate matter samples are 86.2%-110% and 97.1%-113%, respectively. Besides, the limits of detection (LODs) of the target compounds are 0.004-0.020 ng/m3 with the sampling volume of 24 m3, which is much lower compared with accelerated solvent extraction method, because of no solvent extraciton and less target compounds loss. The actual samples of PM2.5 collected in heating season and non heating season in Beijing were determined using this method. The results showed that the target compounds are all detected, and the total concentrations of branched alkane and alkylcyclohexane in heating season are significantly higher than that in the non heating season. Besides, the concentration of branched alkane is two orders of magnitude higher than alkylcyclohexane both in heating season and non heating season. This method is simple and fast, and has great application value in the rapid detection of non polar compounds in particulate matter without complicated pretreatment and organic solvent. -
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[1] 胡敏，何凌燕，黄晓峰，等. 北京大气细粒子和超细粒子理化特征、来源及形成机制[M]. 北京：科学出版社，2009. [2] HE K, YANG F, MA Y, et al. The characteristics of PM2.5, in Beijing, China[J]. Atmospheric Environment, 2001, 35(29): 4959-4970. [3] CASS G R. Organic molecular tracers for particulate air pollution sources[J].Trac Trends in Analytical Chemistry, 1998, 17(6): 356-366. [4] LINGYAN H E, MIN H U, HUANG X, et al. Determination of organic molecular tracers in PM2.5 in the atmosphere of Beijing[J]. Acta Scientiae Circumstantiae, 2005, 25(1): 23-29. [5] 管红香，陈多福，吴能友. 墨西哥湾深水下陆坡区冷泉碳酸岩石中的环烷烃及单环芳烃的特征与来源[J]. 海洋地质与第四纪地质，2010,30(3):113-118.GUAN Hongxiang, CHEN Duofu, WU Nengyou. Distribution and origin of cycloalkane and monocyclicaromatic in seep-carbonates from lower slopes of gulf of mexico[J]. Marine Geology & Quaternary Geology, 2010, 30(3): 113-118(in Chinese). [6] 周树青，黄海平，林畅松，等. 生物标志化合物、早期生命和古环境[J]. 地质论评，2007,53(3):389-396.ZHOU Shuqing, HUANG Haiping, LIN Changsong, et al. Biomarker, earlier life and the concurrent environment[J]. Geological Review, 2007, 53(3): 389-396(in Chinese). [7] 吴征. 广西百色盆底湖相有机质中单环烷烃分布特征及其地化意义浅析[J]. 矿物岩石，1993,13(3):95-99.WU Zheng. The distribution characteristics of monocyclic alkanes in organic matter of lacustrine facies from basic basin in guangxi and their geochemical significance[J]. Journal of Mineralogy and Petrology, 1993, 13(3): 95-99(in Chinese). [8] 周家斌，王铁冠，黄云碧，等. 北京地区大气颗粒物中正构烷烃的粒径分布及污染源示踪研究[J]. 中国石油大学学报：自然科学版，2004,28(5):121-125.ZHOU Jiabin, WANG Tieguan, HUANG Yunbi, et al. Tracing study on pollutants and size distribution of n-alkanes in airborne particles in Beijing area[J]. Journal of the University of Petroleum, China, 2004, 28(5): 121-125(in Chinese). [9] 马海丽，李峣，钱枫，等. 北京市大气颗粒物中正构烷烃污染特征的研究[J]. 环境科学与技术，2013,36(3):50-54.MA Haili, LI Yao, QIAN Feng, et al. Pollution characteristics of n-alkane in aerosol particles of Beijing[J]. Environmental Science & Technology, 2013, 36(3): 50-54(in Chinese). [10] BI X H, SHENG G Y, PENG P A, et al. Distribution of particulate- and vapor-phase n-alkanes and polycyclic aromatic hydrocarbons in urban atmosphere of Guangzhou, China[J]. Atmospheric Environment, 2003, 37(2): 289-298. [11] 姚利，李杏茹，郭雪清，等. 2007年春节期间北京大气细粒子中正构烷烃的污染特征[J]. 环境科学，2009,30(2):589-593.YAO Li, LI Xingru, GUO Xueqing, et al. Pollution characteristics of n-alkanes in atmospheric fine particles during spring festival of 2007 in Beijing[J]. Environmental Science, 2009, 30(2): 589-593(in Chinese). [12] 张枝焕，陶樹，叶必雄，等. 土壤和沉积物中烃类污染物的主要来源于识别标志[J]. 土壤通报，2004,35(6):793-798.ZHANG Zhihuan, TAO Shu, YE Bixiong, et al. Pollution sources and identification of hydrocarbons in soil and sediment using molecular markers[J]. Chinese Journal of Soil Science, 2004, 35(6): 793-798(in Chinese). [13] OROS D R, SIMONEIT B R T. Identification and emission rates of molecular tracers in coal smoke particulate matter[J]. Fuel, 2000, 79(5): 515-536. [14] 唐小玲，倪金龙. 广州大气气溶胶总悬浮颗粒物(TSP)中的有机示踪化合物[J]. 环境化学，2012,31(2):226-234.TANG Xiaoling, NI Jinlong. Determination of organic molecular tracers in total suspended particle (TSP) in the atmosphere of Guangzhou[J]. Environmental Chemistry, 2012, 31(2): 226-234(in Chinese). [15] 何凌燕，胡敏，黄晓锋，等. 北京大气气溶胶PM2.5中的有机示踪化合物[J]. 环境科学学报，2005,25(1):23-29.HE Lingyan, HU Min, HUANG Xiaofeng, et al. Determination of organic molecular tracers in PM2.5 in the atmosphere of Beijing[J]. Acta Scientiae Circumstantiae, 2005, 25(1): 23-29(in Chinese). [16] 方冬青，蔡天骐，张阳，等. 我国机动车和燃油锅炉颗粒有机物排放特征[J]. 化学工业与工程，2015,32(5):44-51.FANG Dongqing, CAI Tianqi, ZHANG Yang, et al. Characters of airborne particular matter from vehicular exhausts and oil-powered boiler-emissions[J]. Chemical Industry and Engineering, 2015, 32(5): 44-51(in Chinese). [17] 贺桃娥，邵龙义，李红，等. 北京市西北城区大气可吸入颗粒物中饱和烃的分布特征[J]. 古地理学报，2004,6(4):485-492.HE Taoe, SHAO Longyi, LI Hong, et al. Distribution of saturated hydrocarbons in airborne inhalable particulates of northwestern urban district in Beijing[J]. Journal of Palaeogeography, 2004, 6(4): 485-492(in Chinese). [18] 袁杨森，刘大锰，车瑞俊，等. 北京夏季大气颗粒物中有机污染源的生物标志物示踪[J]. 中国科学院大学学报，2007,24(5):601-611.YUAN Yangsen, LIU Dameng, CHE Ruijun, et al. Source tracing of biomarkers in the organic pollutants from atmospheric particulates in Beijing city during summer[J]. Journal of University of Chinese Academy of Sciences, 2007, 24(5): 601-611(in Chinese). [19] 郝亮，吴大朋，关亚风. 大气颗粒物中有机物色谱分析的样品制备技术[J]. 色谱，2014,32(9):906-912.HAO Liang, WU Dapeng, GUAN Yafeng. Sample preparation methods for chromatographic analysis of organic components in atmospheric particulate matter[J]. Chinese Journal of Chromatography, 2014, 32(9): 906-912(in Chinese). [20] HAYS M D, LAVRICH R J. Developments in direct thermal extraction gas chromatography-mass spectrometry of fine aerosols[J]. Trac Trends in Analytical Chemistry, 2007, 26(2): 88-102. [21] 王欣欣，刘庆阳，刘艳菊，等. 二级热脱附-气相色谱-质谱联用测定大气可吸入颗粒物中的16种多环芳烃[J]. 色谱，2010,28(9):849-853.WANG Xinxin, LIU Qingyang, LIU Yanju, et al. Determination of 16 polycyclic aromatic hydrocarbons in airborne particle samples using two-step thermal desorption and gas chromatography-mass spectrometry[J]. Chinese Journal of Chromatography, 2010, 28(9): 849-853(in Chinese). [22] 陈冬蕾，何凌燕，黄晓锋，等. 气溶胶中烃类有机物居里点热解析-GC/MS联用分析[J]. 中国环境科学，2011,31(7):1122-1127.CHEN Donglei, HE Lingyan, HUANG Xiao-feng, et al. Analyzing hydrocarbon compounds in aerosols by CPP-GC/MS method[J]. China Environmental Science, 2011, 31(7): 1122-1127(in Chinese). [23] 孟虎，赵景红，段春凤，等. 热解析-气相色谱或气相色谱-质谱法分析大气可吸入颗粒物中的半挥发性有机化合物[J]. 分析化学，2014,42(7):931-936.MENG Hu, ZHAO Jinghong, DUAN Chunfeng, et al. Thermal desorption-gas chromatography or gas chromatography-mass spectrometry for analysis of semi-volatile compounds on atmospheric particulate matters[J]. Chinese Journal of Analytical Chemistry, 2014, 42(7): 931-936(in Chinese). [24] DING L C, KE F, WANG D K W, et al. A new direct thermal desorption-GC/MS method: organic speciation of ambient particulate matter collected in Golden, BC[J]. Atmospheric Environment, 2009, 43(32): 4894-4902.
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