The use of static mass spectrometry to determine the combined stable isotopic composition of small samples of atmospheric methane.

Abstract

Global budgets of atmospheric trace gases are increasingly being constrained by means of stable isotope measurements. Published analytical techniques for studying the parallel stable isotopic composition of methane (delta(13)C and deltaD) require prohibitively large quantities of methane for analysis, making them unsuitable for studies where sample size is small, e.g. soil methane fluxes. A highly sensitive static mass spectrometer has been developed which uniquely uses CH(4) as the analyte. The method requires only 8 ng of CH(4) for analysis (<10 mL ambient air), making replicated measurements of the isotopic composition of CH(4) in small samples feasible for the first time. This paper provides the first detailed description of the instrumentation and the analytical technique. The technique has been used to analyse small samples of air collected in Snowdonia over 21 months. The combined stable isotopic composition (delta(17)M) ranged from 29.5 to 35.5 per thousand, with an average value of 32.2 per thousand, and was strongly correlated with wind direction (p <0.01, r(2) = 0.71). Copyright 1999 John Wiley & Sons, Ltd.