High-precision potassium measurements using laser-induced breakdown spectroscopy under high vacuum conditions for in situ K–Ar dating of planetary surfaces

• We measure potassium with LIBS at low pressures (< 10- 2 Pa) for in situ dating.
• A power law calibration curve is obtained.
• The detection limit of 300 ppm and the quantitation limit of 800 ppm are obtained.
• K–Ar age error would be 10% for 3.5 Ga rocks with 1 wt.% K2O if Ar has ~ 15% errors.
• K can be measured with instruments previously carried in planetary missions.

We conducted a series of laser induced breakdown spectroscopy (LIBS) experiments for K measurements under high vacuum conditions (10- 6 Pa) for the purpose of developing in-situ isochron type K–Ar dating instruments for planetary missions. Unlike whole rock measurement methods, isochron measurements require LIBS experiments in a vacuum chamber because simultaneous Ar isotopic measurements are necessary. However, detailed examination of detection limits and accuracy of this method at low pressures has not been examined extensively before. In this study, the capability of K measurements under high vacuum conditions was examined using LIBS. A compact Czerny-Turner type spectrometer equipped with a charge-coupled device (CCD) as a detector was employed. Twenty-three geologic standard samples were measured using the LIBS method. The second strongest K emission line at 769.89 nm was used for calibration because the strongest emission line at 766.49 nm may suffer from strong interference from another emission line. A calibration curve was constructed for K using internal normalization with the oxygen line at 777 nm and well fitted by a power-law function. Based on the prediction band method, the detection limit and the quantitation limit were estimated to be 300 and 800 ppm, respectively. The 1σ relative uncertainty of the K calibration was 20% for 1 wt.% K2O and 40% for 3000 ppm K2O. If the amount of Ar is measured with 15% error for the 3.5 billion years rocks containing 1 and 0.3 wt.% K2O, the K–Ar ages would be determined with 10% and 20% 1σ errors, respectively. This level of precision will significantly improve the current Martian chronology, which has uncertainty about a factor of two to four. These results indicate that the concentration of K can be measured quantitatively under high vacuum conditions using a combination of instruments that have previously been carried in planetary missions, which suggests the viability of building in situ isochron K–Ar dating instruments with LIBS.