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Journal Article

On-line hydrogen-isotope measurements of organic samples using elemental chromium: an extension for high temperature elemental-analyzer techniques


Brand,  Willi A.
Service Facility Stable Isotope, Dr. W. A. Brand, Max Planck Institute for Biogeochemistry, Max Planck Society;

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Gehre, M., Renpenning, J., Gilevska, T., Qi, H., Coplen, T. B., Meijer, H. A., et al. (2015). On-line hydrogen-isotope measurements of organic samples using elemental chromium: an extension for high temperature elemental-analyzer techniques. Analytical Chemistry, 87(10), 5198-5205. doi:10.1021/acs.analchem.5b00085.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0026-B655-E
The high temperature conversion (HTC) technique using an elemental analyzer with glassy carbon tube and filling (TC/EA) is a widely used method for hydrogen isotopic analysis of water and many solid and liquid organic samples with analysis by isotope-ratio mass spectrometry (IRMS). However, the TC/EA IRMS method may produce inaccurate δ2H results, with values deviating by more than 20 mUr (milliurey = 0.001 = 1 ‰) from the true value for some materials. We show that a single-oven, chromium-filled elemental analyzer coupled to an IRMS substantially improves the measurement quality and reliability for hydrogen isotopic compositions of organic substances (Cr-EA method). Hot chromium maximizes the yield of molecular hydrogen in a helium carrier gas by irreversibly and quantitatively scavenging all reactive elements except hydrogen. In contrast, under TC/EA conditions hetero-atoms like nitrogen or chlorine (and other halogens) can form hydrogen cyanide (HCN) or hydrogen chloride (HCl) and this can cause isotopic fractionation. The Cr-EA technique thus expands the analytical possibilities for on-line hydrogenisotope measurements of organic samples significantly. This method yielded reproducibility values (1-sigma) for δ2H measurements on water and caffeine samples of better than 1.0 and 0.5 mUr, respectively. To overcome handling problems with water as the principal calibration anchor for hydrogen isotopic measurements, we have employed an effective and simple strategy using reference waters or other liquids sealed in silver-tube segments. These crimped silver tubes can be employed in both the Cr-EA and TC/EA techniques. They simplify considerably the normalization of hydrogen-isotope measurement data to the VSMOW-SLAP scale (Vienna Standard Mean Ocean Water-Standard Light Antarctic Precipitation), and their use improves accuracy of the data by eliminating evaporative loss and associated isotopic fractionation while handling water as a bulk sample. The calibration of organic samples, commonly having high δ2H values, will benefit from the availability of suitably 2H-enriched reference waters, extending the VSMOW-SLAP scale above zero.