In-situ K-Ar dating on Mars based on UV-Laser ablation coupled with a LIBS-QMS system: Development, calibration and application of the KArMars instrument

Absolute dating is needed to check and calibrate the relative Martian chronology presently available from meteoritic crater counting. For such purpose, a new analytical system (KArMars) has been developed to experiment the feasibility of in-situ K-Ar for future landing planetary missions. It consists in a laser ablation-based system built to vaporize a reproducible volume of rock. Potassium content is measured by laser-induced breakdown spectroscopy (LIBS) and argon by Quadrupole Mass Spectrometry (QMS). Instrument calibration, and checking of the reliability of the measurements for Martian analyses, requires terrestrial analogues. For such purpose, total chemistry, electron microprobe analyses, flame absorption spectrometry and mass spectrometry have been performed in order to qualify the stoichiometry, the mineralogy, the K concentration and the Ar isotopic composition from a collection of old terrestrial rocks. These new analyses coupled with published data allowed us to select mineral phases (e.g. feldspars, phlogopite, muscovite, amphibole) showing a large range of K content (0.3-8.5 wt%). All these mineral phases display a K-Ar age older than 300 Ma. Hence, the content of radiogenic Ar atoms per gram is within the range of Martian samples (on the order of 1 Ga for 0.4 wt% of K). We have shown that the ablated mass can be precisely estimated by measurement of Ar extracted from a similar mineral of known amount of radiogenic Ar content per gram. Then, it has been possible to derive a well-defined relationship between the ablation time and the sample mass extracted from UV-laser ablations for different minerals. Using an isochron approach from multiple ablations of several samples analyzed as unknowns, we have shown that KArMars can be successfully used for dating samples with different compositions, and with ages varying by an order of magnitude from 0.3 to 3 Ga. In-situ K-Ar ages obtained here for plagioclase and amphibole crystals display uncertainties as low as about 10%, and with accuracy, i.e. difference with the reference age, of only 10%. Such results further support in-situ K-Ar dating based on QMS and LIBS instruments as a reliable approach to be implemented onboard Martian rovers. In case a return mission is made possible, KArMars can also be a valuable tool to select the most relevant samples for return and ensure onsite which samples are representative of most of the surface at a given landing site.