Hyperfine Interactions

, Volume 227, Issue 1–3, pp 259–270 | Cite as

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



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.


Nonlinear optics techniques Resonance ionisation Time of flight mass spectrometry Isotope analysis of noble gases Planetary science Extraterrestrial samples 


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© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  1. 1.School of Physics and AstronomyThe University of ManchesterManchesterUK

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