Precise Determination of Cd Isotope Ratios at 3–10 ng Level by Thermal Ionization Mass Spectrometry Using a Molybdenum Silicide Emitter

Thermal ionization mass spectrometry (TIMS) combined with the double spike technique has excellent analytical precision for Cd isotopic ratio analysis. However, because of the low ionization efficiency of Cd by TIMS, it is still not possible to obtain high precision Cd isotope ratios for small sample size (<100 ng) due to the lack of a highly sensitive emitter for Cd. A new loading method using molybdenum silicide (MoSi₂) emitter has been developed for Cd isotope ratio measurements. This emitter produces a significant enhancement in the ionization efficiency of Cd and thus significantly reduces the required sample size to the 3-10 ng level. Analyses of δ^114/110Cd for the NIST SRM 3108 using ¹⁰⁸Cd-¹¹⁶Cd double spike method show excellent reproducibility (2 SD) that reaches ±0.032‰, ±0.042‰, and ±0.051‰ for 10, 5, and 3 ng of Cd, respectively. This method was further verified with a suite of geological reference materials. Replicate digestions and analyses (<i>n</i> = 8, 2 SD) of δ^114/110Cd for NIST SRM 2711a, NOD A-1, and GBW08401 demonstrated good external reproducibility with results of 0.596 ± 0.024‰ for NIST SRM 2711a, 0.150 ± 0.036‰ for NOD A-1, and -0.665 ± 0.084‰ for GBW08401. These data clearly indicate that MoSi₂ is an excellent alternative for traditional silica gel to Cd isotopic measurements, especially for samples with a low content of Cd.