Isotopic metrology of carbon dioxide. II. Effects of ion source materials, conductance, emission, and accelerating voltage on dual-inlet cross contamination.

We report high-precision isotopic carbon dioxide measurements, made before and after ion source modification to gas isotope ratio mass spectrometry (IRMS) instruments. Measurement protocols were designed to explore the effects of ion source material substitution, source conductance, inlet pressure, electron emission, acceleration potential, and inlet changeover equilibration time. After modification of the IRMS instruments at the National Institute of Standards and Technology (NIST) and the Max-Planck-Institute for Chemistry (MPI-Mainz), immediate changes were observed. At NIST, measurements were no longer sensitive to inlet equilibration times greater than 15 s, and different settings of ion source conductance resulted in delta(13)C shifts of about 0.04 per thousand per 10 per thousand measurement difference between sample and reference, a five-fold improvement. No significant changes in machine performance were observed after a month of use. After a year, performance had degraded slightly, but was controlled by ion source cleaning and the use of low-energy ion acceleration to minimize sputtering. At MPI-Mainz, results were very similar. We report cross-contamination coefficients measured since 1996, and discuss the role of adsorption, ion implantation, and sputtering on cross contamination in mass spectrometry systems. We recommend that users of high-precision IRMS instruments test for and minimize the effects described.