Sub-Model Partial Least Squares for Improved Accuracy in Quantitative Laser Induced Breakdown Spectroscopy
Abstract:One of the primary challenges faced by the ChemCam instrument on the Curiosity Mars rover is developing a regression model that can accurately predict the composition of the wide range of target types encountered (basalts, calcium sulfate, feldspar, oxides, etc.). The original calibration used 69 rock standards to train a partial least squares (PLS) model for each major element. By expanding the suite of calibration samples to >400 targets spanning a wider range of compositions, the accuracy of the model was improved, but some targets with “extreme” compositions (e.g. pure minerals) were still poorly predicted.
We have therefore developed a simple method, referred to as “submodel PLS”, to improve the performance of PLS across a wide range of target compositions. In addition to generating a “full” (0-100 wt.%) PLS model for the element of interest, we also generate several overlapping submodels (e.g. for SiO2, we generate “low” (0-50 wt.%), “mid” (30-70 wt.%), and “high” (60-100 wt.%) models). The submodels are generally more accurate than the “full” model for samples within their range because they are able to adjust for matrix effects that are specific to that range.
To predict the composition of an unknown target, we first predict the composition with the submodels and the “full” model. Then, based on the predicted composition from the “full” model, the appropriate submodel prediction can be used (e.g. if the full model predicts a low composition, use the “low” model result, which is likely to be more accurate). For samples with “full” predictions that occur in a region of overlap between submodels, the submodel predictions are “blended” using a simple linear weighted sum.
The submodel PLS method shows improvements in most of the major elements predicted by ChemCam and reduces the occurrence of negative predictions for low wt.% targets. Submodel PLS is currently being used in conjunction with ICA regression for the major element compositions of ChemCam data.