Resonance ionisation mass spectrometry of krypton and its applications in planetary science

• DOI: 10.1007/s10751-013-0991-6
• Publication Date: 2014-01-08T05:58:57Z
• Authors: I. Strashnov; J. D. Gilmour
• Keywords: planetary science; isotope analysis of noble gases; 13. Climate action; extraterrestrial samples; 0103 physical sciences; nonlinear optics techniques; time of flight mass spectrometry; 7. Clean energy; 01 natural sciences; resonance ionisation

A new resonance ionisation time-of-flight mass spectrometer for determining krypton isotope ratios in extraterrestrial samples is presented. Laser heating is used to extract gas from mg-size samples. A cryogenic sample concentrator is employed. Atoms continuously condense on a 75 K stainless steel substrate at the back plate of a Wiley-McLaren laser ion source from where they are desorbed by a pulsed 1064 nm laser and resonantly ionized in the plume. A three-colour (116.5 nm, 558.1 nm and 1064 nm) excitation scheme is used. Tuneable coherent Vacuum Ultraviolet (vuv) radiation near 116.5 nm is generated by four-wave sum frequency mixing of 252.5 nm and 1507 nm pulsed dye laser beams in a binary mixture of negatively and positively dispersive gases (Xe and Ar). Isotope effects have been observed that reduce the reproducibility of isotope ratio measurements between odd-mass, non-zero nuclear spin isotopes and even-mass, zero nuclear spin isotopes. This can be minimised and stabilised by controlling the laser fluences, experimental geometry, and the population of the magnetic sub-levels of the excited atomic states used in the ionisation process. Once stability is achieved, sample-standard bracketing (during which the known isotope ratios of a standard are determined before and after the measurements of the sample under the same conditions) allows precision and reproducibility of $\sim $ 1 % for the major isotope ratios to be achieved in samples $\sim 10^{6}$ krypton atoms. Detection limits of $<1000$ atoms/isotope have been demonstrated, ratios of $^{81}$ Kr in meteorites have been made with $\sim $ 5–10 % precision. Applications of the instrument in various areas of planetary science are also discussed.