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Post-landing major element quantification using SuperCam laser induced breakdown spectroscopy

Abstract

The SuperCam instrument on the Perseverance Mars 2020 rover uses a pulsed 1064 nm laser to ablate targets at a distance and conduct laser induced breakdown spectroscopy (LIBS) by analyzing the light from the resulting plasma. SuperCam LIBS spectra are preprocessed to remove ambient light, noise, and the continuum signal present in LIBS observations. Prior to quantification, spectra are masked to remove noisier spectrometer regions and spectra are normalized to minimize signal fluctuations and effects of target distance. In some cases, the spectra are also standardized or binned prior to quantification. To determine quantitative elemental compositions of diverse geologic materials at Jezero crater, Mars, we use a suite of 1198 laboratory spectra of 334 well-characterized reference samples. The samples were selected to span a wide range of compositions and include typical silicate rocks, pure minerals (e.g., silicates, sulfates, carbonates, oxides), more unusual compositions (e.g., Mn ore and sodalite), and replicates of the sintered SuperCam calibration targets (SCCTs) onboard the rover. For each major element (SiO 2 , TiO 2 , Al 2 O 3 , FeO T , MgO, CaO, Na 2 O, K 2 O), the database was subdivided into five “folds” with similar distributions of the element of interest. One fold was held out as an independent test set, and the remaining four folds were used to optimize multivariate regression models relating the spectrum to the composition. We considered a variety of models, and selected several for further investigation for each element, based primarily on the root mean squared error of prediction (RMSEP) on the test set, when analyzed at 3 m. In cases with several models of comparable performance at 3 m, we incorporated the SCCT performance at different distances to choose the preferred model. Shortly after landing on Mars and collecting initial spectra of geologic targets, we selected one model per element. Subsequently, with additional data from geologic targets, some models were revised to ensure results that are more consistent with geochemical constraints. The calibration discussed here is a snapshot of an ongoing effort to deliver the most accurate chemical compositions with SuperCam LIBS.

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BibTeXRIS

Ryan B. Anderson, Olivier Forni, Agnes Cousin, Roger C. Wiens, Samuel M. Clegg, Jens Frydenvang, Travis S.J. Gabriel, Ann M. Ollila, Susanne Schröder, Olivier Beyssac, Erin Gibbons, David Vogt, Elise Clave, Jose-Antonio Manrique, Carey Legett, Paolo Pilleri, Raymond Newell, Joseph Sarrao, Sylvestre Maurice, Gorka Arana, Karim Benzerara, Pernelle Bernardi, Sylvain Bernard, Bruno Bousquet, Adrian J. Brown, Cesar Alvarez-Llamas, Baptiste Chide, Edward A. Cloutis, Jade Comellas, Stephanie Connell, Erwin Dehouck, Dorothea Delapp, Ari Essunfeld, Cecile Fabre, Thierry Fouchet, Cristina Garcia, Laura Garcia-Gomez, Patrick J. Gasda, Olivier Gasnault, Elisabeth M. Hausrath, Nina L. Lanza, Javier Laserna, Jeremie Lasue, Guillermo Lopez, Juan Manuel Madariaga, Lucia Mandon, Nicolas Mangold, Pierre-Yves Meslin, Marion Nachon, Anthony Nelson, Horton E. Newsom, Adriana Reyes-Newell, Scott Robinson, Fernando Rull, Shiv Sharma, Justin L. Simon, Pablo Sobron, Imanol Torre Fernandez, Arya Udry, Dawn Venhaus, Scott McLennan, Richard V. Morris, Bethany L. Ehlmann. 2022. Post-landing major element quantification using SuperCam laser induced breakdown spectroscopy. https://doi.org/10.1016/j.sab.2021.106347

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Quantification of manganese for ChemCam Mars and laboratory spectra using a multivariate model

We report a new calibration model for manganese using the laser-induced breakdown spectroscopy instrument that is part of the ChemCam instrument suite onboard the NASA Curiosity rover. The model has been trained using an expanded set of 523 manganese-bearing rock, mineral, metal ore, and synthetic standards. The optimal calibration model uses the Partial Least Squares (PLS) and Least Absolute Shrinkage and Selection Operator (LASSO) multivariate techniques, with a novel “double blending” technique. We determined the detection limit for manganese is 82 ppm using a method blank procedure and is possibly as low as 27 ppm based on visual inspection of the spectra. Based on a representative test set consisting of measurements on 93 standards, the double blended multivariate model shows a Root Mean Squared Error of Prediction (RMSEP) accuracy of 1.39 wt% MnO for the full blended model. Employing a local RMSEP estimate where the model performance is evaluated based on nearby test samples, the accuracy is 0.03 wt% at the quantification limit (0.05 wt% MnO), 0.4 wt% accuracy at 1.0 wt% MnO, and 4.4 wt% accuracy at 100 wt% MnO. Precision is estimated using the standard deviation of the test set measurements, and is ±0.01 wt% MnO at the quantification limit, ±0.09 wt% MnO at 1.0 wt% MnO, and ± 2.1 wt% MnO at 100 wt% MnO (all 1 standard deviation). This new calibration is important for understanding the variation of manganese in the bedrock with the Curiosity rover on Mars, which provides insight into past redox conditions on Mars.

Spectrochimica Acta B