A rapid and precise technique for measuring delta(13)C-CO(2) and delta(18)O-CO(2) ratios at ambient CO(2) concentrations for biological applications and the influence of container type and storage time on the sample isotope ratios.

A simple modification to a commercially available gas chromatograph isotope ratio mass spectrometer (GC/IRMS) allows rapid and precise determination of the stable isotopes ((13)C and (18)O) of CO(2) at ambient CO(2) concentrations. A sample loop was inserted downstream of the GC injection port and used to introduce small volumes of air samples into the GC/IRMS. This procedure does not require a cryofocusing step and significantly reduces the analysis time. The precisions for delta(13)C and delta(18)O of CO(2) at ambient concentration were +/-0.164 and +/-0.247 per thousand, respectively. This modified GC/IRMS was used to test the effects of storage on the (18)O and (13)C isotopic ratios of CO(2) at ambient concentrations in four container types. On average, the change in the (13)C-CO(2) and (18)O-CO(2) ratios of samples after one week of storage in glass vials equipped with butyl rubber stoppers (Bellco Glass Inc.) were depleted by 0.12 and by 0.20 per thousand, respectively. The (13)C ratios in aluminum canisters (Scotty II and IV, Scott Specialty Gasses) after one month of storage were depleted, on average, by 0.73 and 2.04 per thousand, respectively, while the (18)O ratios were depleted by 0.38 and 1.20 per thousand for the Scotty II and IV, respectively. After a month of storage in electropolished containers (Summa canisters, Biospheric Research Corporation), the (13)C-CO(2) and (18)O-CO(2) ratios were depleted, on average, by 0.26 and enriched by 0.30 per thousand, respectively, close to the precision of measurements. Samples were collected at a mature hardwood forest for CO(2) concentration determination and isotopic analysis. A comparison of CO(2) concentrations determined with an infrared gas analyzer and from sample voltages, determined on the GC/IRMS concurrent with the isotopic analysis, indicated that CO(2) concentrations can be determined reliably with the GC/IRMS technique. The (13)C and (18)O ratios of nighttime ecosystem-respired CO(2), determined from the intercept of Keeling plots, were -26.11 per thousand (V-PDB) and -8.81 per thousand (V-PDB-CO(2)), respectively.