Detection and identification of salts and frozen salt solutions combining laser-induced breakdown spectroscopy and multivariate analysis methods: A study for future martian exploration

For the geochemical investigation of extraterrestrial surfaces laser-induced breakdown spectroscopy (LIBS) has been suggested as a powerful analytical tool, and is part of the payload on NASA’s rover Curiosity, which reached Mars in August 2012. Apart from soil in general, LIBS is capable of analyzing ice and salts within the soil. This study demonstrates the feasibility of LIBS for investigating and differentiating between different salts by applying three multivariate analysis (MVA) techniques. The focus was on the capability of the MVA techniques for LIBS data to discriminate between sulfates and chlorides with cations of the same kind as pure pressed pellets and in frozen salt solutions. Two data sets of LIBS spectra of eight different salts (CaCl2, CaSO4, KCl, K2SO4, MgCl2, MgSO4, NaCl, Na2SO4), pure and as frozen salt solutions, were acquired in a dedicated simulation chamber under martian atmospheric conditions. With principal components analysis (PCA) both data sets were analyzed with the aim of dividing the spectra of the ices into groups and revealing the most important lines in the spectra for discrimination and identification of the type of salt. PCA performance is improved by selecting the most relevant lines with emphasis on the sulfur and chlorine lines and additionally averaging the spectra before analysis. Moreover, a subsequent PCA with a subset of data can improve the discrimination ability for a sulfate and a chloride with the same type of cation. Soft independent modeling of class analogy (SIMCA) and partial least squares discriminant analysis (PLS-DA) were performed for both data sets. While SIMCA worked well for the pressed salt samples, its application to the spectra of the frozen salt solutions was not successful. A local PLS-DA of the LIBS spectra of salts with the same cation is capable of distinguishing sulfate and chloride.