An optimized calibration procedure for determining elemental ratios using laser-induced breakdown spectroscopy.

A novel procedure to determine elemental ratios by laser-induced breakdown spectroscopy is presented. This procedure, which we name optimized calibration (OC-LIBS), is a hybrid between empirical methods like calibration curves or chemometrics and the theoretical calibration-free LIBS method (Ciucci, A.; Corsi, M.; Palleschi, V.; Rastelli, S.; Salvetti, A.; Tognoni, E. Appl. Spectrosc. 1999, 53, 960-964) and seeks to reduce the high sensitivity to matrix effects seen when using, e.g., calibration curves by employing the mathematical framework of the calibration-free LIBS method. The OC-LIBS procedure is calibrated using 22 different certified powdered reference samples, spanning numerous different rock types as well as a large variation in the elemental composition. Using the OC-LIBS procedure, the compositional ratios between Mg and the elements Al, Ca, Fe, K, Na, Si, and Ti are calculated using an absolute minimum of sample preparation. A correlation between the reference and calculated values of R(2) ≥ 0.91 and a median relative prediction error ranging between 9.5% and 33% are achieved, despite this diverse set of samples and limited sample preparation. With total data processing times below 1 s, the OC-LIBS procedure allows for all the unique features of LIBS to be utilized, including the ability to provide very fast realtime in situ analyses.

An integrated view of the chemistry and mineralogy of martian soils.

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Dust deposition on the decks of the Mars Exploration Rovers: 10 years of dust dynamics on the Panoramic Camera calibration targets.

The Panoramic Cameras on NASA's Mars Exploration Rovers have each returned more than 17,000 images of their calibration targets. In order to make optimal use of this data set for reflectance calibration, a correction must be made for the presence of air fall dust. Here we present an improved dust correction procedure based on a two-layer scattering model, and we present a dust reflectance spectrum derived from long-term trends in the data set. The dust on the calibration targets appears brighter than dusty areas of the Martian surface. We derive detailed histories of dust deposition and removal revealing two distinct environments: At the Spirit landing site, half the year is dominated by dust deposition, the other half by dust removal, usually in brief, sharp events. At the Opportunity landing site the Martian year has a semiannual dust cycle with dust removal happening gradually throughout two removal seasons each year. The highest observed optical depth of settled dust on the calibration target is 1.5 on Spirit and 1.1 on Opportunity (at 601 nm). We derive a general prediction for dust deposition rates of 0.004 ± 0.001 in units of surface optical depth deposited per sol (Martian solar day) per unit atmospheric optical depth. We expect this procedure to lead to improved reflectance-calibration of the Panoramic Camera data set. In addition, it is easily adapted to similar data sets from other missions in order to deliver improved reflectance calibration as well as data on dust reflectance properties and deposition and removal history.