Stable hydrogen isotopic analysis of nanomolar molecular hydrogen by automatic multi-step gas chromatographic separation

We have developed a new automated analytical system that employs a continuous flow isotope ratio mass spectrometer to determine the stable hydrogen isotopic composition (δD) of nanomolar quantities of molecular hydrogen (H2) in an air sample. This method improves previous methods to attain simpler and lower‐cost analyses, especially by avoiding the use of expensive or special devices, such as a Toepler pump, a cryogenic refrigerator, and a special evacuation system to keep the temperature of a coolant under reduced pressure. Instead, the system allows H2 purification from the air matrix via automatic multi‐step gas chromatographic separation using the coolants of both liquid nitrogen (77 K) and liquid nitrogen + ethanol (158 K) under 1 atm pressure. The analytical precision of the δD determination using the developed method was better than 4‰ for >5 nmol injections (250 mL STP for 500 ppbv air sample) and better than 15‰ for 1 nmol injections, regardless of the δD value, within 1 h for one sample analysis. Using the developed system, the δD values of H2 can be quantified for atmospheric samples as well as samples of representative sources and sinks including those containing small quantities of H2, such as H2 in soil pores or aqueous environments, for which there is currently little δD data available. As an example of such trace H2 analyses, we report here the isotope fractionations during H2 uptake by soils in a static chamber. The δD values of H2 in these H2‐depleted environments can be useful in constraining the budgets of atmospheric H2 by applying an isotope mass balance model. Copyright © 2011 John Wiley & Sons, Ltd.