Gas chromatography flow rates for determining deuterium/hydrogen ratios of natural gas by gas chromatography/high‐temperature conversion/isotope ratio mass spectrometry

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 δ D 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 δ D 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. Copyright © 2008 John Wiley & Sons, Ltd.