Performance evaluation of elemental analysis/isotope ratio mass spectrometry methods for the determination of the D/H ratio in tetramethylurea and other compounds--results of a laboratory inter-comparison.

Tetramethylurea (TMU) with a certified D/H ratio is the internal standard for Site-specific Natural Isotope Fractionation measured by Nuclear Magnetic Resonance (SNIF-NMR) analysis of wine ethanol for detection of possible adulterations (Commission Regulation 2676/90). A new batch of a TMU certified reference material (CRM) is currently being prepared. Whereas SNIF-NMR has been employed up to now, Elemental Analysis/Isotope Ratio Mass Spectrometry ((2)H-EA-IRMS) was envisaged as the method of choice for value assignment of the new CRM, as more precise (better repeatable) data might be obtained, resulting in lower uncertainty of the certified value. In order to evaluate the accuracy and intra- and inter-laboratory reproducibility of (2)H-EA-IRMS methods, a laboratory inter-comparison was carried out by analysing TMU and other organic compounds, as well as some waters. The results revealed that experienced laboratories are capable of generating robust and well comparable data, which highlights the emerging potential of IRMS in food authenticity testing. However, a systematic bias between IRMS and SNIF-NMR reference data was observed for TMU; this lack of data consistency rules out the (2)H-IRMS technique for the characterisation measurement of the new TMU CRM.

Conversion of carbon into CF4 for SI-traceable measurements of absolute carbon isotope amount ratios: a feasibility study.

The feasibility of performing SI-traceable carbon isotope amount ratio measurements following conversion of carbon into CF4 was studied. A procedure for the direct fluorination of carbon with elemental fluorine was developed, and the conversion step was checked for losses, blank contributions, and the absence of systematic isotope effects. Gas chromatography was used to identify and quantify the gaseous fluorination products and to isolate CF4 from byproducts. After fluorination of graphite carbon, CF4 and perfluoroalkanes with up to six carbon atoms were observed as reaction products. Within an uncertainty of 10%, the graphite carbon was fully recovered in the gaseous carbon fluorides, with the main product being CF4 (80-90%) and C2F6 as the major byproduct. The fluorination and GC procedures were found to introduce an alteration not bigger than 0.03 +/- 0.04/1000 on the isotopic composition of CF4. Carbon blank contributions introduced during the fluorination procedure were below 0.5% relative to a typical sample of 4 mg of carbon. For two of the materials investigated, the carbon isotope ratios measured on a differential mass spectrometer were reproducible within a standard deviation of approximately 0.1/1000 for several individual fluorinations. For these materials, the developed fluorination procedure is a straightforward process, which can be used as a foundation to establish SI-traceable measurements of carbon isotope amount ratios. However, for the third graphite material the formation of byproducts (C2F6-C6F14) was found to induce significant isotopic fractionation.