Compound-specific bromine isotope analysis of methyl bromide using gas chromatography hyphenated with inductively coupled plasma multiple-collector mass spectrometry

Methyl bromide is the most important natural bromine contributor to stratospheric ozone depletion, yet there are still large uncertainties regarding quantification of its sources and sinks. The stable bromine isotope composition of CH3Br is potentially a powerful tool to apportion its sources and to study both its transport and its reactive fate. A novel compound-specific method to measure Br-81/Br-79 isotope ratios in CH3Br using gas chromatography hyphenated with inductively coupled plasma multiple-collector mass spectrometry (GC/MCICPMS) was developed. Sample amounts of >40 ng could bemeasured with a precision of 0.1 parts per thousand (1 sigma, n=3). The method results are reproducible over the long term as shown with 36 analyses acquired over 3 months, yielding a standard deviation ( 1s) better than 0.4 parts per thousand. This new method demonstrates for the first time Br isotope ratio determination in gaseous brominated samples. It is three orders of magnitude more sensitive than previously existing isotope ratio mass spectrometry methods for Br isotope determination of other organobromines, thus allowing applications towards ambient atmospheric samples. Copyright (C) 2011 John Wiley & Sons, Ltd.