A method for carbon stable isotope analysis of methyl halides and chlorofluorocarbons at pptv concentrations

A pre-concentration system has been validated for use with a gas chromatography/mass spectrometry/isotope ratio mass spectrometer (GC/MS/IRMS) to determine ambient air 13C/12C ratios for methyl halides (MeCl and MeBr) and chlorofluorocarbons (CFCs). The isotopic composition of specific compounds can provide useful information on their atmospheric budgets and biogeochemistry that cannot be ascertained from abundance measurements alone. Although pre-concentration systems have been previously used with a GC/MS/IRMS for atmospheric trace gas analysis, this is the first study also to report system validation tests. Validation results indicate that the pre-concentration system and subsequent separation technologies do not significantly alter the stable isotopic ratios of the target methyl halides, CFC-12 (CCl2F2) and CFC-113 (C2Cl3F3). Significant, but consistent, isotopic shifts of -27.5 to -25.6 do occur within the system for CFC-11 (CCl3F), although the shift is correctible. The method presented has the capacity to separate these target halocarbons from more than 50 other compounds in ambient air samples. Separation allows for the determination of stable carbon isotope ratios of five of these six target trace atmospheric constituents within ambient air for large volume samples (10 L). Representative urban air analyses from Belfast City are also presented which give carbon isotope results similar to published values for 13C/12C analysis of MeCl (-39.1) and CFC-113 (-28.1). However, this is the first paper reporting stable carbon isotope signatures for CFC-11 (-29.4) and CFC-12 (-37.0).

Stable hydrogen isotope ratios of lignin methoxyl groups as a palaeoclimate proxy

• Stable isotope ratios of organic compounds are valuable tools for determining the geographical origin, identity, authenticity or history of samples from a vast range of sources such as sediments, plants and animals, including humans. • Hydrogen isotope ratios (d2H values) of methoxyl groups in lignin from wood of trees grown in different geographical areas were measured using compound-specificpyrolysis isotope ratio mass spectrometry analysis. • Lignin methoxyl groups were depleted in 2H relative to both meteoric water andwhole wood. A high correlation (r2=0.91) was observed between the d2 H valuesof the methoxyl groups and meteoric water, with a relatively uniform fractionation of –216±19 recorded with respect to meteoric water over a range of d2H values from –110 in northern Norway to + 20‰ in Yemen. Thus, woods from northernlatitudes can be clearly distinguished from those from tropical regions. By contrast, the d2H values of bulk wood were only relatively poorly correlated (r 2 = 0.47) with those of meteoric water. • Measurement of the d 2H values of lignin methoxyl groups is potentially a powerful tool that could be of use not only in the constraint of the geographical origin of lignified material but also in paleoclimate, food authenticity and forensic investigations.

Stable isotope analysis of archived roach (Rutilus rutilus) scales for retrospective study of shallow lake responses to nutrient reduction

1. There is increasing interest in the use of stable isotope analysis of archived materials to study the long-term impacts of lake perturbations, including nutrient manipulation or species invasion. We tested the utility of this approach in a shallow productive lake using the zooplanktivorous early life stages of roach ( Rutilus rutilus), a fish species that is widespread throughout Eurasian lakes.