Haruhisa Tabata

In-situ analysis of major elements using laser-induced breakdown spectroscopy (LIBS) is essential for future lunar landing missions, yet its performance under lunar conditions remains not fully understood. This uncertainty arises from the absence of an atmosphere and the diverse range of surface materials, which vary in chemical composition from anorthosites to basalts, and in physical properties from fine regolith to boulders. To address these challenges, we developed and cross-validated a multivariate LIBS calibration model by measuring 169 compressed fine powders of geologic samples under vacuum. These samples fully encompass the bulk composition range of lunar meteorites. We investigated the applicability of the model to a wider range of samples by measuring lunar meteorites, terrestrial anorthites, and lunar simulants in various physical forms, including rock chips and soils with different grain sizes and bulk densities. For powder samples, the quantification accuracy, assessed using root mean squared error (RMSE), resulted in 2.5 wt% SiO2, 0.25 wt% TiO2, 1.2 wt% Al2O3, 1.3 wt% MgO, 1.2 wt% CaO, 0.33 wt% Na2O, 0.47 wt% K2O (0.060 wt% K2O in the <1 wt% range), and 1.5 wt% T-Fe2O3. For rock chip samples, the RMSEs were 3.1 wt% SiO2, 0.32 wt% TiO2, 2.2 wt% Al2O3, 2.5 wt% MgO, 2.0 wt% CaO, 0.33 wt% Na2O, 0.089 wt% K2O, and 2.1 wt% T-Fe2O3. Despite significant differences in physical conditions between powders and rocks, their RMSEs remained consistent within a factor of two. Changes in grain size or bulk density of soils had relatively minor effects on the RMSE. These RMSEs confirm that the quantification accuracy of LIBS is sufficient to distinguish the subgroups within the lunar anorthosite suite (e.g., anorthosites vs. norites) and basalts (e.g., high-Ti vs. low-Ti) across a range of soil types, from coarse to fine and from loose to compact, as well as rocks. Furthermore, our analysis shows that LIBS can differentiate between “purest” and “pure” anorthosites (98 and 95 vol% plagioclase, respectively) based on the 3σ detection limits of Mg and Fe lines. These capabilities of LIBS align well with the goals of future lunar exploration, such as locating ilmenite-rich soils for resource extraction, detecting purest anorthosites to understand early lunar evolution, and identifying noritic impact melts to refine lunar chronology. Overall, our results demonstrate that LIBS serves as a versatile tool for rapid geochemical characterization on the Moon.

Mars has experienced drastic environmental evolution in terms of pH, redox, and desiccation. NASA's Curiosity rover discovered that the sediments of the Pahrump Hills member of the Murray formation in Gale Crater contained different redox states of Fe oxides. To interpret the observations, understanding the factors that control iron redox states within early Gale lakes on Mars is needed. Here, we present the results of a one-dimensional geochemical model of a closed-basin lake that considers the Fe(II) photo-oxidation reaction. Depending on the source of Fe(II) (groundwater vs. river flow), lake pH, advection rate, and atmospheric composition, we defined four types of chemical profiles in the lake; namely, Fe(II) dominated, Fe(III) dominated, carbonate precipitating, and redox-stratified profiles. The Fe(III) dominated profile corresponds to the end member case in which photo-oxidation effectively oxidizes the supplied Fe(II). The redox-stratified profile, interpreted as an intermediate condition between Fe(III) dominated profile and Fe(II) dominated profile, appears in broad parameter set when Fe(II) is supplied from the groundwater, typically with a low to moderate Fe(II) input flux at acidic to alkaline pH (pH 5–9) conditions; however, the low water flux due to the nature of the groundwater may be unable to explain the measured abundance of Fe oxides in the sediments. Another endmember case, the Fe(II) dominated profile, which would also be expected to generate mixed valence Fe oxides, occurs when the pH is acidic (pH 4–5); nevertheless, the acidic pH is inconsistent with the mineral assemblages of the sediments. Carbonate precipitating profiles were limited to the case in which Fe(II) is supplied by groundwater with high Fe input flux and alkaline pH of 8–9. These results may imply either the Fe(II) input flux was high enough for the redox-stratified case or Fe(II) photo-oxidation was suppressed by turbidity or by dusty/cloudy atmosphere, or possibly that Fe(II) oxides found in the Pahrump Hills member are, at least partly, of detrital origin. Although numerous other factors (ex., effect of lake depth, variable pH throughout the lake water, detailed chemical speciation) remain unconsidered, the diverse profiles in Fe redox resulting from Fe(II) photo-oxidation reaction sheds light on interpreting the variety and the evolution of redox condition on early Mars.