大气有机物热脱附-全二维气相色谱-火焰离子化分析方法

全二维气相色谱（GC×GC）是20世纪90年代发展起来的具有高分辨率、高灵敏度、高峰容量等优势的分离技术,在我国将其用于大气挥发性有机物（VOCs）研究方面才刚刚起步.本文将GC-GC与氢火焰离子化检测器（FID）联用,构建了用于测量大气有机物的热脱附-全二维气相色谱-氢火焰离子化分析系统（TD-GC×GC-FID）.采用HP-5MS和HP-INNOWAX色谱柱,建立了C5-C15大气有机物分析方法,实现了一次分析过程同时分离非甲烷烃（NMHCs）、含氧挥发性有机物（OVOCs）和卤代烃等多种组分.利用标准物质和四级杆质谱（qMS）进行定性,外标法结合FID质量校正因子定量.目标物在GC-GC谱图中第一和第二维保留时间变化分别小于0.6s和0.02s,峰体积平均相对标准偏差为14.3%,其中烷烃和芳香烃为4.5%.标准曲线r2均值大于0.99,平均检出限为6.04ng,平均回收率为111%.利用该方法检测到2010年1月北京市区大气中400多种有机物（信噪比大于50）,鉴定了其中的103种物质,包括烷烃、烯烃、芳香烃、卤代烃、醛、酮、酯、醇和醚等.所测定有机物平均总浓度为51.3×10-9V/V,其中OVOCs约占51%,芳香烃约占30%,烷烃约占15%,卤代烃和烯烃分别占3%和1%.平均浓度最高的前3个组分是乙醇（9.84×10-9V/V）、丙酮（6.72×10-9V/V）和甲苯（3.48×10-9V/V）.     

兰州市和太原市环境空气中NMHCs的碳同位素组成特征

研究了兰州市和太原市环境空气中非甲烷烃(NMHCs)的污染状况及来源。利用Tenax-TA吸附管采样,热解析-色谱-同位素质谱联用仪(TD-GC-IRMS)测定了两个城市夏季不同功能区环境空气中NMHCs的稳定碳同位素组成。得出,兰州市和太原市居民区苯的δ(13C)分别为-26.4‰和-25.0‰;正烷烃的δ(13C)分别为-33.9‰~-26.1‰,-32.8‰~-27.4‰;两市交通枢纽区环境空气中检测出的C4—C7之间的NMHCs化合物相同,δ(13C)相差不大,兰州市为-30.8‰~-25.6‰,太原市为-31.0‰~-26.4‰。结果表明,两市交通枢纽区苯主要来源于汽车尾气和油类挥发,工业区石化行业类主要排放的NMHCs污染物为苯和烷烃类化合物,电厂等大型企业主要排放异丁烯、顺-2-戊烯等。控制汽车尾气、油类挥发、工业排放是降低环境空气中NMHCs污染的关键。     

The effect of treating air samples with magnesium perchlorate for water removal during analysis for non-methane hydrocarbons

A comparison has been made between two cryogenic preconcentration - high resolution gas chromatography techniques for the analysis of non-methane hydrocarbons in ambient air, one involving treatment of air samples with magnesium perchlorate to remove water, the other involving analysis without treatment. Recoveries of C₁-, C₂-, and C₃-substituted benzenes in treated samples were 80%, 50%, and 50%, respectively. Incomplete recovery of C₇-C₉ n-1-olefins was also observed. C₂-C₈ hydrocarbons and C₂-C₆ n-1-olefins were recovered with greater than 90% efficiency. Analyses of certified audit samples containing a mixture of C₂-C₈ aliphatic and aromatic hydrocarbons at the 20 ppbv level in humidified zero-grade air indicated that the accuracy of the technique for untreated air samples was approximately 90%. The use of magnesium perchlorate for water removal cannot be recommended for the analysis of non-methane hydrocarbons in ambient air.     

Development of a Dual Capillary Column GC Method for the Trace Determination of C2–C9 Hydrocarbons in Ambient Air

An analytical method based on a dual capillary gas chromatographic technique combining the advantages of GasPro PLOT and a non polar narrow bore WCOT column was developed for the analysis of air samples containing C2–C9 NMHCs. A refocusing step was not required due to the fast heating rate of the sample preconcentration trap and the resolving power of the PLOT column for C2 and C3 NMHCs. Water had to be removed from the air samples to avoid plugging of the columns if the initial GC oven temperature was below ambient temperature. To dry air samples, a scrubber and a cryogenic technique were employed. The interferences caused by carbon dioxide were reduced by purging the loaded sample preconcentration trap with helium. The dual column system was compared to a method employing a refocusing device and a single narrow bore WCOT column. Both systems provided a high degree of precision. However, the dual column approach was superior to the single column system due to better resolution of low molecular weight components.     

Multisorbent tubes sampling used in thermal desorption cold trap injection with gas chromatography-mass spectrometry for C2–C6 hydrocarbon measurements in an urban atmosphere

Three solid adsorbents (Carbotrap, Carbotrap C, and Carbosieve III) were evaluated for sampling trace non-methane hydrocarbons in urban atmospheres. The sampled atmosphere was pumped through a multisorbent tube containing the three sorbents separated by a small amount of silanized glass wool. The trapped compounds were recovered by thermal desorption and analysed by combining cryogenic enrichment with gas chromatography and mass spectrometry. Adsorption/thermal desorption and breakthrough experiments were performed to test their ability to quantitatively trap the light hydrocarbons. The technique was suitable for determination of low ppbv concentrations of these compounds. Ambient atmospheric sampling was conducted in Vitoria-Gasteiz (Basque Country, Spain), and the measurements cover a period of one year (2001–2002). Fifteen C₂–C₆ hydrocarbons are identified and quantified, and seasonal trends are discussed.     

兰州市大气中NMHCs的稳定碳同位素组成及来源

利用Tenax TA吸附管采集了兰州市污染源和主要功能区冬季及夏季大气样品, 利用热解析-气相色谱-同位素质谱联用仪分析了样品中非甲烷烃的稳定碳同位素组成。结果表明: 不同源排放的 NMHCs 的稳定碳同位素组成不同, 交通相关源中NMHCs的δC平均值为 - 28. 7‰, 显著低于燃煤烟气(-24.1‰); 夏季各功能区NMHCs 的δ¹³C值相差不大, 平均值在 - 29. 5‰ ～- 27. 4‰之间, 冬季西固工业区的 δ¹³C平均值(-25. 5‰)大于盘旋路(-28. 8‰) 和二电厂(-31. 2‰)。同位素来源分析结果显示: 盘旋路冬夏两季 NMHCs主要来源于交通相关源; 西固工业区冬季 NMHCs 主要来源于燃煤烟气, 夏季正烷烃和苯主要来源于交通相关源;二电厂冬季正戊烷、正己烷和苯等主要来源于交通相关源; 居民区夏季 NMHCs 则受到交通相关源排放的影响较大, 其他未知源也有贡献。冬夏两季大气中均检测出苯的存在, 且主要来源于交通相关源, 因此控制交通相关源的排放是降低致癌物质苯污染的关键。