Trace Element Concentrations from the Mars Exploration Rover Alpha Particle X-Ray Spectrometers: Implications for the Geologic Histories of Meridiani Planum and Gusev Crater

The Alpha Particle X-ray Spectrometers (APXS) onboard the Mars Exploration Rovers (MER) Spirit and Opportunity interrogated the bedrock, soil, and regolith at Gusev crater and Meridiani Planum, respectively. The APXS derives the composition of geologic materials through a combination of particle-induced X-ray emission (PIXE) and X-ray fluorescence (XRF) spectroscopy. Each measurement results in a histogram of energies with characteristic peak areas proportional to elemental concentrations. This spectrum reflects not only the composition of a target but also varies with experimental conditions (e.g., measurement duration, mission age, standoff, temperature), which must be accounted for to accurately quantify the elements present in a spectrum. Individual APXS measurements often provide sufficient counting statistics to resolve and quantify major, minor, and select trace elements (e.g., Ni, Zn, Br) while others (e.g., Ga, Ge) are more difficult to precisely quantify due to, in part, their typical low concentrations (e.g., sub-30 µg/g).

To combat the effect of statistical noise on trace element quantification, individual spectra are summed together to create a composite spectrum. We have assembled a database of target characteristics, such as target type (e.g., rock, soil), location, feature, target, formation, and degree of sample preparation (e.g., as-is, brushed, abraded), for each individual APXS spectrum. Spectra of targets with shared geological context and geochemical characteristics (e.g., ratio of Fe³⁺ to Fe_T) were summed to create meaningful combinations of individual spectra (i.e., composite spectrum). The composite spectra were fit with a simplified (i.e., Gaussian peaks with a linear background) nonlinear least squares fitting routine to identify promising composites for quantification with the fitting routine developed and utilized for the quantification of other elements within MER APXS spectra. Composite spectra were also assessed visually and quantitatively to confirm they were representative of trace element peaks within each of the individual spectra rather than outliers.

At both Meridiani Planum and Gusev crater, results indicate that the concentrations of Ga and Ge in outcrops are more than an order of magnitude higher than expected from meteoritic contribution alone. The ratios of Ga to Al and Ge to Si can also be used to infer the geologic history of a region due to their similar ionic radii and charges and therefore geochemical behavior. The Ga/Al molar ratio tends to be much more consistent at Meridiani Planum compared to that of Ge/Si, which shows more variation between formations. The divergence of the behaviors of Ge and Si could be explained by high temperature diagenetic fluids, as could the consistent behaviors of Ga and Al. We conclude that the elevated concentrations of trace elements such as Ga and Ge may be sourced in part from volcanic outgassing, and regional trends in the molar ratios of Ga/Al and Ge/Si are potentially due to high temperature diagenetic fluids.