Improved analysis of micro- and nanomole-scale sulfur multi-isotope compositions by gas source isotope ratio mass spectrometry.

RATIONALE: Multiple sulfur isotope compositions are usually measured on relatively large samples (in the range of micromoles); however, sometimes only small amounts are available and thus it is necessary to analyze small (sub-micromole) samples. We report an improved method to measure multiple sulfur isotope compositions: δ(33) S, δ(34) S and δ(36) S values on the SF6 molecule (m/z 127, 128, 129, 131) for quantities down to 0.1 micromole, and δ(33) S and δ(34) S values for quantities down to 20 nanomoles. METHODS: Multiple sulfur isotope analyses including fluorination and purification of two international Ag2 S standards, IAEA-S1 and IAEA-S3, were carried out at various low concentrations on a dual-inlet isotope ratio mass spectrometer using a microvolume and modified resistor capacities. RESULTS: The analyses yielded a narrow range of δ(34) S values vs CDT (the international standard), with an overall standard deviation of ±0.2 ‰, which was within the range of certified values. This demonstrates the feasibility of determining both Δ(33) S and Δ(36) S values on the sub-micromole scale, and Δ(33) S values on the nanomole scale with similar accuracy to conventional dual-inlet analyses. CONCLUSIONS: The analysis of the three S-isotope ratios on the SF6 molecule using the so-called conventional fluorination method and dual-inlet ion ratio mass spectrometry is reliable for sample sizes down to ~20 nanomoles. Despite being close to the theoretical limits for maintaining the viscous flow regime of gas in the capillary, errors were not limited by counting statistics, but probably relate to sample gas purification. Copyright © 2016 John Wiley & Sons, Ltd.

Oxygen and nitrogen isotopic fractionations during human respiration.

Both oxygen and nitrogen isotope compositions (delta18O and delta15N) of exhaled air from 10 individuals were measured. Results show linear relations between isotope variation and the fraction of O2 used during the respiration process. The isotopic influence of physiological parameters such as smoking habits, age, haemoglobin count, oxygen fixation rate or physical exercise was assessed. Among them, only smoking habits do not have any effect on delta18O. Delta15N differences between inhaled and exhaled air may indicate an active (but minor) role for nitrogen during the human respiration process. Nevertheless, nitrogen fractionation is homogenous among all the individuals, which is coherent with the fact that nitrogen metabolism is controlled by the intestinal bacterial activity.