ChemCam Instrument Research Articles

Ensemble methods for quantification of potassium oxide in ChemCam Mars and laboratory spectra

In this paper we test new approaches for predicting the amount of element oxides in rock samples from the ChemCam instrument suite onboard the NASA Curiosity rover by focusing on K2O. Using the expanded dataset compiled by Gasda et al. (2021) with and without the Earth to Mars (E2M and NoE2M) transformation discussed in Clegg et al. (2017) we trained blended submodels using the “double blending” technique and compared these to ensemble methods (Random Forest, ExtraTrees, and Gradient Boosting Regression). We found that ensemble methods performed similar to blended submodels when looking at RMSE-P on the laboratory spectra and provided significant advantages when looking at spectra coming from Mars. For the full model, blended submodels achieved an RMSE-P of 0.62 and 0.60 (E2M and NoE2M respectively) while Gradient Boosting Regression resulted in a slightly improved RMSE-P of 0.59 and 0.60. More importantly, by employing a local RMSE-P estimation technique where model performance is evaluated based on nearby test samples we found that using ensemble methods can lower the quantification limit for K2O from the current value of ≈0.6 wt% to ≈0.08 wt% using Extra Trees and Random Forest. This would allow for a much larger range of K2O values to be quantified on Mars with greater certainty given that most targets seen on Mars tend to have <1 wt% K2O. Finally, we used both Mean Decrease in Impurity (MDI) and permutation importance techniques to investigate the wavelengths used by the ensemble methods and found that they correspond to known potassium emission lines. This suggests that ensemble methods can provide an easier to train and improved alternative to blended submodels for predicting potassium compositions from Laser Induced Breakdown Spectroscopy (LIBS) data.

Mechanical properties of terrestrial analogs to calcium sulfate veins on Gale crater, Mars

The MSL (Mars Science Lab) Curiosity rover has documented the presence of natural fractures at the Gale crater on Mars. Through the utilization of the ChemCam instrument, the chemical composition of the veins on Mars has been analyzed, revealing their mineralogy as calcium sulfate. However, there is limited knowledge regarding the mechanical properties of these veins, which hinders a deeper understanding of their origin. This work aims to characterize the mechanical properties of gypsiferous Triassic Moenkopi mudrocks as the terrestrial rock analog to Mars. The Digital Image Correlation (DIC) technique was used in tandem with the Indirect Tensile Strength test to acquire the required spatial full-field strain maps for characterizing the fracture propagation with complex geometries in addition to the derived mechanical properties. The effect of the primary vein orientation on the exerted load on the load-strain profile, fracture initiation and propagation, and tensile strength was established. The dynamic spatial horizontal, vertical, and shear strains' progression was distinguished through DIC imaging. The key findings include: (1) Different failure modes were observed in samples with and without calcium sulfate veins, with higher tensile strength perpendicular to lamination; (2) Most samples with veins exhibited reduced tensile strength, except when oriented 90° to the load; (3) Fracture paths were influenced by the orientation angle, with irregular paths at certain angles and more regular paths for centrally located veins; (4) Digital image correlation revealed a fracture process zone before macro-crack initiation and subsequent shear crack propagation; (5) Shear strain accumulation preceded shear crack propagation, with potential initiation of tensile cracks.

Detection of Copper by the ChemCam Instrument Along Curiosity's Traverse in Gale Crater, Mars: Elevated Abundances in Glen Torridon

AbstractLaser‐induced breakdown spectroscopy, as utilized by the ChemCam instrument onboard the Curiosity rover, detected enhanced abundances of the element copper. Since landing in Gale crater (6 August 2012), 10 enhancements in copper abundance were observed during 3007 Martian days (sols) of rover operations and 24 km of driving (as of 20 January 2021). The most prominent ones were found in the Kimberley area on the crater floor (Aeolis Palus) and in Glen Torridon (GT) on the lower flanks of Aeolis Mons (Mt. Sharp). Enhancements in copper record the former existence of modestly acidic and oxidizing fluids, which were more oxidizing in Kimberley than in GT. Of the two main types of bedrock in the lowest part of GT, Mg‐rich “coherent” and K‐rich “rubbly” (named based on their outcrop expression), copper was detected only in coherent, not in rubbly bedrock. The difference between these two types of bedrock may be due to difference in provenance. Alternatively, based on a recently developed lacustrine‐groundwater mixing model, we suggest that rubbly bedrock was altered by modestly acidic, shallow‐subsurface lake water that leached out both copper and manganese, while coherent bedrock was affected by dominantly alkaline fluids which would be consistent with its mineralogical composition (including siderite) as returned by the CheMin instrument onboard the rover. Higher up in GT, ChemCam data indicated significant gradients in the copper concentration in coherent bedrock on a local scale of only a few meters, which suggests a different alteration style and possibly different types of diagenetic fluids.

The Mars Microphone Onboard SuperCam

The Mars Microphone is one of the five measurement techniques of SuperCam, an improved version of the ChemCam instrument that has been functioning aboard the Curiosity rover for several years. SuperCam is located on the Rover's Mast Unit, to take advantage of the unique pointing capabilities of the rover's head. In addition to being the first instrument to record sounds on Mars, the SuperCam Microphone can address several original scientific objectives: the study of sound associated with laser impacts on Martian rocks to better understand their mechanical properties, the improvement of our knowledge of atmospheric phenomena at the surface of Mars: atmospheric turbulence, convective vortices, dust lifting processes and wind interactions with the rover itself. The microphone will also help our understanding of the sound signature of the different movements of the rover: operations of the robotic arm and the mast, driving on the rough floor of Mars, monitoring of the pumps, etc ... The SuperCam Microphone was delivered to the SuperCam team in early 2019 and integrated at the Jet Propulsion Laboratory (JPL, Pasadena, CA) with the complete SuperCam instrument. The Mars 2020 Mission launched in July 2020 and landed on Mars on February 18th 2021. The mission operations are expected to last until at least August 2023. The microphone is operating perfectly.

Askival: An altered feldspathic cumulate sample in Gale crater.

Askival is a light-toned, coarsely crystalline float rock, which was identified near the base of Vera Rubin Ridge in Gale crater. We have studied Askival, principally with the ChemCam instrument but also using APXS compositional data and MAHLI images. Askival and an earlier identified sample, Bindi, represent two rare examples of feldspathic cumulate float rocks in Gale crater with >65% relict plagioclase. Bindi appears unaltered whereas Askival shows textural and compositional signatures of silicification, along with alkali remobilization and hydration. Askival likely experienced multiple stages of alteration, occurring first through acidic hydrolysis of metal cations, followed by deposition of silica and possible phyllosilicates at low T and neutral-alkaline pH. Through laser-inducedbreakdownspectroscopy compositional analyses and normative calculations, we suggest that an assemblage of Fe-Mg silicates including amphibole and pyroxene, Fe phases, and possibly Mg-rich phyllosilicate are present. Thermodynamic modeling of the more pristine Bindi composition predicts that amphibole and feldspar are stable within an upper crustal setting. This is consistent with the presence of amphibole in the parent igneous rocks of Askival and suggests that the paucity of amphiboles in other known Martian samples reflects the lack of representative samples of the Martian crust rather than their absence on Mars.

Bedrock Geochemistry and Alteration History of the Clay‐Bearing Glen Torridon Region of Gale Crater, Mars

AbstractGlen Torridon is a topographic trough located on the slope of Aeolis Mons, Gale crater, Mars. It corresponds to what was previously referred to as the “clay‐bearing unit,” due to the relatively strong spectral signatures of clay minerals (mainly ferric smectites) detected from orbit. Starting in January 2019, the Curiosity rover explored Glen Torridon for more than 700 sols (Martian days). The objectives of this campaign included acquiring a detailed understanding of the geologic context in which the clay minerals were formed, and determining the intensity of aqueous alteration experienced by the sediments. Here, we present the major‐element geochemistry of the bedrock as analyzed by the ChemCam instrument. Our results reveal that the two main types of bedrock exposures identified in the lower part of Glen Torridon are associated with distinct chemical compositions (K‐rich and Mg‐rich), for which we are able to propose mineralogical interpretations. Moreover, the topmost stratigraphic member exposed in the region displays a stronger diagenetic overprint, especially at two locations close to the unconformable contact with the overlying Stimson formation, where the bedrock composition significantly deviates from the rest of Glen Torridon. Overall, the values of the Chemical Index of Alteration determined with ChemCam are elevated by Martian standards, suggesting the formation of clay minerals through open‐system weathering. However, there is no indication that the alteration was stronger than in some terrains previously visited by Curiosity, which in turn implies that the enhanced orbital signatures are mostly controlled by non‐compositional factors.

Evidence for Amorphous Sulfates as the Main Carrier of Soil Hydration in Gale Crater, Mars

AbstractUnderstanding the genesis of Martian soils is important to constrain the hydrogeologic history of the planet. Soils have the potential to record paleoenvironmental conditions, through the nature of secondary minerals formed during weathering. In situ X‐ray diffraction analyses in Gale crater have revealed that about one third of each soil sample is composed of amorphous materials containing hydrated phases. Here, we use the geochemical data from the ChemCam instrument to investigate the nature and origin of the hydrated amorphous phases. We report for the first time with ChemCam clues for the presence of sulfates within the amorphous component of soils. We show that sulfates are the main carrier of the soil hydration and possibly explain the nature of hydrogen and sulfur measured from orbit. These sulfates and the apparent lack of significant Al‐bearing weathering products are consistent with a model of soil formation including weathering of olivine in water‐limited acidic conditions.

From Lake to River: Documenting an Environmental Transition Across the Jura/Knockfarril Hill Members Boundary in the Glen Torridon Region of Gale Crater (Mars).

Between January 2019 and January 2021, the Mars Science Laboratory team explored the Glen Torridon (GT) region in Gale crater (Mars), known for its orbital detection of clay minerals. Mastcam, Mars Hand Lens Imager, and ChemCam data are used in an integrated sedimentological and geochemical study to characterize the Jura member of the upper Murray formation and the Knockfarril Hill member of the overlying Carolyn Shoemaker formation in northern GT. The studied strata show a progressive transition represented by interfingering beds of fine‐grained, recessive mudstones of the Jura member and coarser‐grained, cross‐stratified sandstones attributed to the Knockfarril Hill member. Whereas the former are interpreted as lacustrine deposits, the latter are interpreted as predominantly fluvial deposits. The geochemical composition seen by the ChemCam instrument show K2O‐rich mudstones (∼1–2 wt.%) versus MgO‐rich sandstones (>6 wt.%), relative to the average composition of the underlying Murray formation. We document consistent sedimentary and geochemical data sets showing that low‐energy mudstones of the Jura member are associated with the K‐rich endmember, and that high‐energy cross‐stratified sandstones of the Knockfarril Hill member are associated with the Mg‐rich endmember, regardless of stratigraphic position. The Jura to Knockfarril Hill transition therefore marks a significant paleoenvironmental change, where a long‐lived and comparatively quiescent lacustrine setting progressively changes into a more energetic fluvial setting, as a consequence of shoreline regression due to either increased sediment supply or lake‐level drop.

From machine learning to transfer learning in laser-induced breakdown spectroscopy analysis of rocks for Mars exploration

With the ChemCam instrument, laser-induced breakdown spectroscopy (LIBS) has successively contributed to Mars exploration by determining the elemental compositions of soils, crusts, and rocks. The American Perseverance rover and the Chinese Zhurong rover respectively landed on Mars on February 18 and May 15, 2021, further increase the number of LIBS instruments on Mars. Such an unprecedented situation requires a reinforced research effort on the methods of LIBS spectral data analysis. Although the matrix effects correspond to a general issue in LIBS, they become accentuated in the case of rock analysis for Mars exploration, because of the large variation of rock compositions leading to the chemical matrix effect, and the difference in surface physical properties between laboratory standards (in pressed powder pellet, glass or ceramic) used to establish calibration models and natural rocks encountered on Mars, leading to the physical matrix effect. The chemical matrix effect has been tackled in the ChemCam project with large sets of laboratory standards offering a good representation of various compositions of Mars rocks. The present work more specifically deals with the physical matrix effect which is still lacking a satisfactory solution. The approach consists in introducing transfer learning in LIBS data treatment. For the specific application of total alkali-silica (TAS) classification of rocks (either with a polished surface or in the raw state), the results show a significant improvement in the ability to predict of pellet-based models when trained together with suitable information from rocks in a procedure of transfer learning. The correct TAS classification rate increases from 25% for polished rocks and 33.3% for raw rocks with a machine learning model, to 83.3% with a transfer learning model for both types of rock samples.

Long-Distance 3D Reconstructions Using Photogrammetry with Curiosity’s ChemCam Remote Micro-Imager in Gale Crater (Mars)

The Mars Science Laboratory rover Curiosity landed in Gale crater (Mars) in August 2012. It has since been studying the lower part of the 5 km-high sedimentary pile that composes Gale’s central mound, Aeolis Mons. To assess the sedimentary record, the MSL team mainly uses a suite of imagers onboard the rover, providing various pixel sizes and fields of view from close to long-range observations. For this latter, we notably use the Remote Micro Imager (RMI), a subsystem of the ChemCam instrument that acts as 700 mm-focal length telescope, providing the smallest angular pixel size of the set of cameras on the Remote Sensing Mast. The RMI allows observations of remote outcrops up to a few kilometers away from the rover. As retrieving 3D information is critical to characterize the structures of the sedimentary deposits, we describe in this work an experiment aiming at computing for the first time with RMI Digital Outcrop Models of these distant outcrops. We show that Structure-from-Motion photogrammetry can successfully be applied to suitable sets of individual RMI frames to reconstruct the 3D shape and relief of these distant outcrops. These results show that a dedicated set of observations can be envisaged to characterize the most interesting geological features surrounding the rover.

Geochemical Analysis Using Laser-Induced Breakdown Spectroscopy

Laser-induced breakdown spectroscopy (LIBS) is an ideal method for elemental analysis of geological samples. Although X-ray fluorescence (XRF) can measure a wide variety of elements, it struggles to measure elements lighter than silicon, meaning that many key crustal elements cannot be measured. In addition, as a fast, standoff method, LIBS can be employed in a variety of geometries with various distances from the target. LIBS has famously been employed by the National Aeronautics and Space Administration (NASA) on their Mars rovers, first in the ChemCam instrument and now in the SuperCam instrument. This article summarizes both the basic methodology and the most successful calibration and quantification methods to date.

Improving ChemCam LIBS long-distance elemental compositions using empirical abundance trends

The ChemCam instrument on the Curiosity rover provides chemical compositions of Martian rocks and soils using remote laser-induced breakdown spectroscopy (LIBS). The elemental calibration is stable as a function of distance for Ti, Fe, Mg, and Ca. The calibration shows small, systematically increasing abundance trends as a function of distance for Al, Na, K, and to some extent, Si. The distance effect is known to be due to a dependence with distance on the relative strengths of atomic transition lines. Emission lines representing transitions from relatively low energy levels remain intense at longer distances while emission lines representing transitions from higher energy levels decrease in intensity more rapidly as a function of distance. The multivariate algorithms used to determine elemental compositions rely on a large number of emission lines in many cases, so rather than trying to correct all emission lines, a study was made of the predicted compositions as a function of distance, in order to determine an empirical correction. Abundance trends can be well approximated by a linear trend with distance within the ranges of abundances and distances observed up to ~6 m. Data from 11 distinct geological members and data groups of the Murray formation in Gale crater, Mars, were used to form the model, selecting the members and data groups yielding the best statistics. The model was tested using data from several targets observed from two different distances, and using data from the Kimberley formation, the composition of which is significantly different from the Murray formation, showing that the model works on other compositions beyond those used to build the model. For long-distance observations up to ~6 m, corrections can be made back to an equivalent composition at the median distance of ChemCam observations (2.6 m). The model has been validated up to 6.2 m, although ChemCam is able to observe bedrock targets to >7 m, and iron meteorites to distances of >9 m.

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.

Laser-Induced Breakdown Spectroscopy (LIBS) characterization of granular soils: Implications for ChemCam analyses at Gale crater, Mars

The Curiosity rover has been characterizing mineralogical and chemical compositions of Gale crater soils on Mars since 2012. Given its sub-millimeter scale of analysis, the ChemCam instrument is well suited to study the composition of soil constituents. However, the interpretation of LIBS data on soils in the martian environment is complicated by the large diversity of particle sizes (from dust to sand), combined with the unknown physical arrangement of their mineral constituents (i.e., the type of grain mixtures). For example, martian soils contain a significant amount of X-ray amorphous materials whose physical form remains unclear. In this study, we reproduced martian soil analyses in the laboratory to understand how the LIBS technique can provide specific insights into the physical and chemical properties of granular soils. For this purpose, different types of samples were studied with various ranges of grain sizes, mimicking two possible mixtures that may occur in martian soils: mechanical mixtures of two populations of grains made of distinct chemical compositions; and material forming a compositionally distinct coating at the surface of grains. Our results, also supported by in situ ChemCam data, demonstrate that both the sizes and the type of mixture of soil particles have a strong influence on the LIBS measurement. For mechanical mixtures of two populations of grains larger than 125–250 μm, the scatter of the data provides information about the chemical composition of the end-members. On the other hand, the chemistry recorded by LIBS for grains with surface coatings is fully dominated by the outer material for grains smaller than 500 μm in diameter. This is due to the small penetration depth of the laser (~0.3–1.5 μm per shot), combined with the ejection of small grains at each shot, which leads to a constant replenishment of fresh material. This experimental work will thus improve our understanding of martian soils analyzed by ChemCam, and more broadly, will benefit LIBS studies of granular materials.

The Chemostratigraphy of the Murray Formation and Role of Diagenesis at Vera Rubin Ridge in Gale Crater, Mars, as Observed by the ChemCam Instrument

AbstractGeochemical results are presented from Curiosity's exploration of Vera Rubin ridge (VRR), in addition to the full chemostratigraphy of the predominantly lacustrine mudstone Murray formation up to and including VRR. VRR is a prominent ridge flanking Aeolis Mons (informally Mt. Sharp), the central mound in Gale crater, Mars, and was a key area of interest for the Mars Science Laboratory mission. ChemCam data show that VRR is overall geochemically similar to lower‐lying members of the Murray formation, even though the top of VRR shows a strong hematite spectral signature as observed from orbit. Although overall geochemically similar, VRR is characterized by a prominent decrease in Li abundance and Chemical Index of Alteration across the ridge. This decrease follows the morphology of the ridge rather than elevation and is inferred to reflect a nondepositionally controlled decrease in clay mineral abundance in VRR rocks. Additionally, a notable enrichment in Mn above baseline levels is observed on VRR. While not supporting a single model, the results suggest that VRR rocks were likely affected by multiple episodes of postdepositional groundwater interactions that made them more erosionally resistant than surrounding Murray rocks, thus resulting in the modern‐day ridge after subsequent erosion.

Boron and Lithium in Calcium Sulfate Veins: Tracking Precipitation of Diagenetic Materials in Vera Rubin Ridge, Gale Crater

AbstractThe NASA Curiosity rover's ChemCam instrument suite has detected boron in calcium‐sulfate‐filled fractures throughout the sedimentary strata of Gale crater including Vera Rubin ridge. The presence of elevated B concentration provides insights into Martian subsurface aqueous processes. In this study we extend the data set of B in Ca‐sulfate veins across Gale crater, comparing the detection frequency and relative abundances with Li. We report 33 new detections of B within veins analyzed between Sols 1548 and 2311 where detections increase in Pettegrove Point and Jura members, which form Vera Rubin ridge. The presence of B and Li in the Ca‐sulfate veins is possibly due to dissolution of preexisting B in clays of the bedrock by acids or neutral water and redistribution of the elements into the veins. Elevated frequency of B detection in veins of Gale crater correlates with presence of dehydration features such as desiccation cracks, altered clay minerals and detections of evaporites such as Mg‐sulfates and chloride salts in the host rocks. The increased observations of B also coincide with decreased Li concentration in the veins (average Li concentration of veins drops by ~15 ppm). Boron and Li have varying solubilities, and Li does not form salts as readily upon dehydration as B, causing it to remain in the solution. So the weak negative correlation between B and Li may reflect the crystallization sequence during dehydration on Vera Rubin ridge.

Mars Science Laboratory Observations of Chloride Salts in Gale Crater, Mars.

The Mars Science Laboratory Curiosity rover is traversing a sequence of stratified sedimentary rocks in Gale crater that contain varied eolian, fluviodeltaic, and lake deposits, with phyllosilicates, iron oxides, and sulfate salts. Here, we report the chloride salt distribution along the rover traverse. Chlorine is detected at low levels (<3 wt.%) in soil and rock targets with multiple MSL instruments. Isolated fine‐scale observations of high chlorine (up to ≥15 wt.% Cl), detected using the ChemCam instrument, are associated with elevated Na2O and interpreted as halite grains or cements in bedrock. Halite is also interpreted at the margins of veins and in nodular, altered textures. We have not detected halite in obvious evaporitic layers. Instead, its scattered distribution indicates that chlorides emplaced earlier in particular members of the Murray formation were remobilized and reprecipitated by later groundwaters within Murray formation mudstones and in diagenetic veins and nodules.

Insights of the Qualified ExoMars Laser and Mechanical Considerations of Its Assembly Process

1960 is the birth year of both the laser and the Mars exploration missions. Eleven years passed before the first successful landing on Mars, and another six before the first rover could explore the planet’s surface. In 2011, both technologies were reunited with the first laser landing on Mars as part of the ChemCam instrument, integrated inside the Curiosity Rover. In 2020, two more rovers with integrated lasers are expected to land on Mars: one through the National Aeronautics and Space Administration (NASA) Mars 2020 mission and another through the European Space Agency (ESA) ExoMars mission. The ExoMars mission laser is one of the components of the Raman Spectrometer instrument, which the Aerospace Technology National Institute of Spain (INTA) is responsible for. It uses as its excitation source a laser designed by Monocrom and manufactured in collaboration with the Fraunhofer Institute for Applied Optics and Precision Engineering (IOF). In this paper, we present for the first time the final flight module laser that has been installed in the rover’s onboard laboratory and validated to be shipped to Mars in 2020. Particular emphasis is given to mechanical considerations and assembly procedures, as the ExoMars laser assembly has required soldering techniques in contrast to the standard adhesive technologies used for most laser assembly processes in order to fulfill the environmental and optical requirements of the mission.

Copper enrichments in the Kimberley formation in Gale crater, Mars: Evidence for a Cu deposit at the source

Copper quantification with laser induced breakdown spectroscopy (LIBS) using a univariate calibration model enables the ChemCam instrument onboard the Curiosity rover to measure unusually elevated Cu concentrations in potassic sandstones and Mn-oxide-bearing fracture fills in the Kimberley region of Gale crater, Mars. Mostly, the copper phases occurring in sedimentary bedrock are associated with detrital silicates, including feldspars, pyroxenes and K-phyllosilicates, likely coming from a potassic igneous source near the northern crater rim, while those present in the fractures are likely adsorbed on the surface of manganese oxides. These two different mineralogical associations imply at least two distinct processes: Cu enrichment in bedrock at the source, likely during crystallization of the igneous silicates, and adsorption of Cu on Mn-oxides precipitated from groundwater that encountered oxidizing conditions within fractures in the bedrock. The potassic sediments enriched in copper may be evidence of a porphyry copper deposit or an impact-induced hydrothermal deposit in the source region.

Variable selection in laser-induced breakdown spectroscopy assisted by multivariate analysis: An alternative to multi-peak fitting

When Laser-Induced Breakdown Spectroscopy (LIBS) spectra exhibit complex spectral features as the result of two or more overlapping emission lines, it is common to apply multi-peak fitting in order to extract the relevant information. In this paper, we propose an alternative method to multi-peak fitting based on advanced data processing. To illustrate this new strategy, we consider the quantification of lithium from a series of spectra related to samples being part of the calibration samples for the ChemCam instrument dedicated to the analysis of Mars geological matrices. In this case, one can observe a spectral overlap between the unresolved doublet of lithium at 670.78 and 670.79 nm and the line of calcium at 671.769 nm. A first PLS model built from 1713 variables related to the spectral range 492.7–856.8 nm revealed the strong influence of this doublet of lithium but also a significant overfitting and instabilities preventing from any exploitation of this model. Reducing the number of variables to 17 corresponding to the spectral window 669.07–672.49 nm then allowed to build a 3-component PLS model characterized by the apparently satisfying indicators, R2 = 0.95 and RMSECV = 11 ppm. However, this model was not considered as satisfying due to the significant nonlinearity between LIBS signal and concentration values, which it was unable to describe, since it is linear by definition. Thus, our PLS model was exploited through the loading weights plot of the first component, explaining >84% of the variance of the lithium concentration values, which allowed to select the 9 variables exhibiting the highest correlation with the lithium concentration values. Then, the sum of the related values of intensity was exploited to build a univariate quadratic model, characterized by R2 = 0.93 and RMSECV = 17 ppm. Comparing this result with the previous results obtained after multi-peak fitting, namely R2 = 0.92 and RMSECV = 18 ppm, we conclude that our alternative approach can be considered as a satisfactory option.