Laser induced breakdown spectroscopy on soils and rocks: Influence of the sample temperature, moisture and roughness

ExoMars, ESA's next mission to Mars, will include a combined Raman/LIBS instrument for the comprehensive in-situ mineralogical and elemental analyses of Martian rocks and soils. It is inferred that water exists in the upper Martian surface as ice layers, “crystal” water or adsorbed pore water. Thus, we studied Laser Induced Breakdown Spectroscopy (LIBS) on wet and dry rocks under Martian environmental conditions in the temperature range − 60 °C to + 20 °C and in two pressure regimes, above and below the water triple point. Above this point, the LIBS signals from the rock forming elements have local minima that are accompanied by hydrogen (water) emission maxima at certain temperatures that we associate with phase transitions of free or confined water/ice. At these sample temperatures, the plasma electron density and its temperature are slightly lowered. In contrast to powder samples, a general increase of the electron density upon cooling was observed on rock samples. By comparing the LIBS signal behavior from the same rock with different grades of polishing, and different rocks with the same surface treatment, it was possible to distinguish between the influence of surface roughness and the bulk material structure (pores and grains). Below the triple point of water, the LIBS signal from the major sample elements is almost independent of the sample temperature. However, at both considered pressures we observed a hydrogen emission peak close to − 50 °C, which is attributed to a phase transition of supercooled water trapped inside bulk pores.