Contribution of a martian atmosphere to laser-induced breakdown spectroscopy (LIBS) data and testing its emission characteristics for normalization applications

Abstract

For in-situ geochemical analysis of the surface of Mars, laser-induced breakdown spectroscopy (LIBS) is a very useful technique and the first extraterrestrial LIBS instrument ChemCam will soon be followed by others. Appropriate normalization of real mission data that is taken under varying experimental and environmental conditions from diverse geologic samples is an ongoing topic. One approach is the scaling to emission line intensities of carbon and oxygen from the CO2-dominated low-pressure martian atmosphere as an internal standard. Here, we performed several experiments to examine the emission of carbon and oxygen from a simulated martian atmosphere on simple, mostly mono-elemental samples, and to compare the emission characteristics of the elements of both origins. Differences in laser irradiance were found to have the biggest impact on sample emission lines scaled to C and O emission of the atmosphere. The temporal behavior shown in time-resolved LIBS measurements is dominated by the degree of ionization, but the ratio of the neutral emission from the sample to neutral emission from the atmosphere also varies over time. The effect of different grain sizes was minor in comparison to the high intrinsic variation in the LIBS data. Different samples were found to affect the absolute intensity of atmospheric C(I) more than O(I). Furthermore, the C(I) emission was found to be inseparably superimposed by iron if the latter was present in the target. The results indicate limitations of the general suitability of atmospheric carbon and oxygen emission for normalization purposes of martian LIBS data.