Nancy Thomas

Characterization of LIBS emission lines for the identification of chlorides, carbonates, and sulfates in salt/basalt mixtures for the application to MSL ChemCam data: LIBS OF CL, C, S IN SALT-BASALT MIXTURES

Ancient environmental conditions on Mars can be probed through the identification of minerals on its surface, including water-deposited salts and cements dispersed in the pore space of sedimentary rocks. Laser-induced breakdown spectroscopy (LIBS) analyses by the Martian rover Curiositys ChemCam instrument can indicate salts, and ChemCam surveys aid in identifying and selecting sites for further, detailed in situ analyses. We performed laboratory LIBS experiments under simulated Mars conditions with a ChemCam-like instrument on a series of mixtures containing increasing concentrations of salt in a basaltic background to investigate the potential for identifying and quantifying chloride, carbonate, and sulfate salts found only in small amounts, dispersed in bulk rock with ChemCam, rather than concentrated in veins. Data indicate that the presence of emission lines from the basalt matrix limited the number of Cl, C, and S emission lines found to be useful for quantitative analysis; nevertheless, several lines with intensities sensitive to salt concentration were identified. Detection limits for the elements based on individual emission lines ranged from ~20 wt % carbonate (2 wt % C), ~5–30 wt % sulfate (1–8 wt % S), and ~5–10 wt % chloride (3–6 wt % Cl) depending on the basaltic matrix and/or salt cation. Absolute quantification of Cl, C, and S in the samples via univariate analysis depends on the cation-anion pairing in the salt but appears relatively independent of matrices tested, following normalization. These results are promising for tracking relative changes in the salt content of bulk rock on the Martian surface with ChemCam.

Characterization of Hydrogen in Basaltic Materials With Laser‐Induced Breakdown Spectroscopy (LIBS) for Application to MSL ChemCam Data

The Mars Science Laboratory rover, Curiosity, is equipped with ChemCam, a laser‐induced breakdown spectroscopy (LIBS) instrument, to determine the elemental composition of nearby targets quickly and remotely. We use a laboratory sample set including prepared mixtures of basalt with systematic variation in hydrated mineral content and compositionally well‐characterized, altered basaltic volcanic rocks to measure hydrogen by characterizing the H‐alpha emission line in LIBS spectra under Martian environmental conditions. The H contents of all samples were independently measured using thermogravimetric analysis. We found that H peak area increases with weight percent H for our laboratory mixtures with basaltic matrices. The increase is linear with weight percent H in the mixtures with structurally bound H up to about 1.25 wt.% H and then steepens for higher H‐content samples, a nonlinear trend not previously reported but potentially important for characterizing high water content materials. To compensate for instrument, environmental, and target matrix‐related effects on quantification of H content from the LIBS signal, we examined multiple normalization methods. The best performing methods utilize O 778‐ and C 248‐nm emission lines. The methods return comparable results when applied to ChemCam data of H‐bearing materials on Mars. The calibration and normalization methods tested here will aid in investigations of H by LIBS on Mars with ChemCam and SuperCam. Further laboratory work will aid quantification across different physical matrices and heterogeneous textures because of differences we observed in H in pelletized and natural rock samples of the same composition.