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The isotopic composition of volatile organic compounds (VOCs) can providevaluable information on their sources and fate not deducible from mixingratios alone. In particular the reported carbon stable isotope ratios ofchloromethane and bromomethane from different sources cover aδ13C-range of almost 100‰ making isotope ratios a very promising toolfor studying the biogeochemistry of these compounds. So far, thedetermination of the isotopic composition of C1 and C2 halocarbons othersthan chloromethane is hampered by their low mixing ratios. In order to determine the carbon isotopic composition of C1 and C2halocarbons with mixing ratios as low as 1 pptv (i) a field suitablecryogenic high volume sampling system and (ii) a chromatographic set up forprocessing these samples have been developed and validated. The samplingsystem was tested at two different sampling sites, an urban and a coastallocation in Northern Germany. The average δ13C-values forbromomethane at the urban site were −42.9 ± 1.1‰ and agreed well withpreviously published results. But at the coastal site bromomethane wassubstantially enriched in 13C by almost 10‰. Less pronounceddifferences were observed for chlorodifluoromethane, 1,1,1-trichloroethaneand chloromethane. We suggest that these differences are related to theturnover of these compounds in ocean surface waters. Furthermore we reportfirst carbon isotope ratios for iodomethane (−40.4‰ to −79.8‰), bromoform(−13.8‰ to 22.9‰), and other halocarbons

A high volume sampling system for isotope determination of volatile halocarbons and hydrocarbons