Jia Wanglu, Peng Ping'an, Liu Jinzhong
State Key Laboratory of Organic Geochemistry (SKLOG), Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou, GD 510640, P.R. China.
Rapid Commun Mass Spectrom. 2008 Aug;22(16):2521-5. doi: 10.1002/rcm.3641.
The effects of the gas chromatography flow rate on the determination of the deuterium/hydrogen (D/H) ratios of natural gas utilising gas chromatography/high-temperature conversion/isotope ratio mass spectrometry (GC/TC/IRMS) have been evaluated. In general, the measured deltaD values of methane, ethane and propane decrease with increase in column flow rate. When the column flow rate is 1 mL/min or higher, which is commonly used for the determination of D/H ratios of natural gas, the organic H in gas compounds may not be completely converted into hydrogen gas. Based on the results of experiments conducted on a GC column with an i.d. of 0.32 mm, a GC flow rate of 0.6 mL/min is proposed for determining the D/H ratios of natural gas by GC/TC/IRMS. Although this value may be dependent on the instrument conditions used in this work, we believe that correct deltaD values of organic compounds with a few carbon atoms are obtained only when relatively low GC flow rates are used for D/H analysis by GC/TC/IRMS. Moreover, as the presence of trace water could significantly affect the determination of D/H ratios, a newly designed inlet liner was used to remove trace water contained in some gas samples.
评估了气相色谱流速对采用气相色谱/高温转换/同位素比质谱法(GC/TC/IRMS)测定天然气中氘/氢(D/H)比的影响。一般来说,甲烷、乙烷和丙烷的测量δD值随柱流速增加而降低。当柱流速为1 mL/min或更高时(这是测定天然气D/H比常用的流速),气体化合物中的有机氢可能无法完全转化为氢气。基于内径为0.32 mm的气相色谱柱的实验结果,建议采用0.6 mL/min的气相色谱流速通过GC/TC/IRMS测定天然气的D/H比。尽管该值可能取决于本工作中使用的仪器条件,但我们认为只有在通过GC/TC/IRMS进行D/H分析时使用相对较低的气相色谱流速,才能获得含几个碳原子的有机化合物的正确δD值。此外,由于痕量水的存在会显著影响D/H比的测定,因此使用了新设计的进样衬管来去除一些气体样品中所含的痕量水。