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 (H(2)) 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 H(2) 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 H(2) can be quantified for atmospheric samples as well as samples of representative sources and sinks including those containing small quantities of H(2) , such as H(2) in soil pores or aqueous environments, for which there is currently little δD data available. As an example of such trace H(2) analyses, we report here the isotope fractionations during H(2) uptake by soils in a static chamber. The δD values of H(2) in these H(2)-depleted environments can be useful in constraining the budgets of atmospheric H(2) by applying an isotope mass balance model.