RATIONALEThe geologic history of the Solar System builds on an extensive record of impact flux models, crater counts, and ∼270 kg of lunar samples analyzed in terrestrial laboratories. However, estimates of impactor flux may be biased by the fact that most of the dated Apollo samples were only tenuously connected to an assumed geologic context. Moreover, uncertainties in the modeled cratering rates are significant enough to lead to estimated errors for dates on Mars and the Moon of ∼1 Ga. Given the great cost of sample return missions, combined with the need to sample multiple terrains on multiple planets, we have developed a prototype instrument that can be used for in situ dating to better constrain the age of planetary samples.METHODSWe demonstrate the first use of laser ablation resonance ionization mass spectrometry for 87Rb-87Sr isochron dating of geological specimens. The demands of accuracy and precision have required us to meet challenges including regulation of the ambient temperature, measurement of appropriate backgrounds, sufficient ablation laser intensity, avoidance of the defocusing effect of the plasma created by ablation pulses, and shielding of our detector from atoms and ions of other elements.RESULTSTo test whether we could meaningfully date planetary materials, we have analyzed a piece of the Martian meteorite Zagami. In each of four separate measurements we obtained 87Rb-87Sr isochron ages for Zagami consistent with its published age, and, in both of two measurements that reached completion, we obtained better than 200 Ma precision. Combining all our data into a single isochron with 581 spot analyses gives an 87Rb-87Sr age for this specimen of 360 ±90 Ma.CONCLUSIONSOur analyses of the Zagami meteorite represent the first successful application of resonance ionization mass spectrometry to isochron geochronology. Furthermore, the technique is miniaturizable for spaceflight and in situ dating on other planetary bodies. © 2014 The Authors. Rapid Communications in Mass Spectrometry published by John Wiley & Sons, Ltd.

RationaleWe report new 87Rb‐87Sr isochron data for the Duluth Gabbro, obtained with a laser ablation resonance ionization mass spectrometer that is a prototype spaceflight instrument. The gabbro has a Rb abundance and a range of Rb/Sr ratios that are similar to those of KREEP‐rich basalts found on the nearside of the Moon. Dating of previously un‐sampled young lunar basalts, which generally have a KREEP‐rich composition, is critical for understanding the bombardment history of the Moon since 3.5 Ga, which in turn informs the chronology of the solar system. Measurements of lunar analogs like the Duluth Gabbro are a proof of concept for in situ dating of rocks on the Moon to constrain lunar history.MethodsUsing the laser ablation resonance ionization mass spectrometer we ablated hundreds of locations on a sample, and at each one measured the relative abundances of the isotopes of Rb and Sr. A delay between the resonant photoionization processes separates the elements in time, eliminating the potential interference between 87Rb and 87Sr. This enables the determination of 87Rb‐87Sr isochron ages without sophisticated sample preparation that would be impractical in a spaceflight context.ResultsWe successfully dated the Duluth Gabbro to 800 ± 300 Ma using traditional isochron methods like those used in our earlier analysis of the Martian meteorite Zagami. However, we were able to improve this to 1100 ± 200 Ma, an accuracy of <1σ, using a novel normalization approach. Both these results agree with the age determined by Faure et al. in 1969, but our novel normalization improves our precision.ConclusionsDemonstrating that this technique can be used for measurements at this level of difficulty makes ~32% of the lunar nearside amenable to in situ dating, which can complement or supplement a sample return program. Given these results and the scientific value of dating young lunar basalts, we have recently proposed a spaceflight mission called the Moon Age and Regolith Explorer (MARE). © 2015 The Authors and Southwest Research Institute. Rapid Communications in Mass Spectrometry published by John Wiley & Sons Ltd.

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Sequential photon-excitation, electron-impact ionization with subsequent mass analysis has been applied to a barium atomic beam. High-resolution, Doppler-free laser excitation produces the 6s6p(1)P(1) excited state, which is then ionized by electron bombardment. The excited state is selectively ionized when bombardment energies are between the excited- and ground-state ionization thresholds. Mass discrimination has permitted the recording of individual optical spectra for all the stable isotopes, including the 0.1% abundant (130)Ba and (132)Ba, in a sample with natural isotopic abundances.

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