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The Mars 2020 Perseverance rover landed on February 18, 2021, and has started ground operations. The ExoMars

Producción Científica, The Europa lander is a concept for a potential future planetary exploration mission which purpose is to characterize the icy shell of Europa and to search for organics. To achieve this objective, the current concept of the lander includes a Raman spectrometer, such as RLS instrument, that could be able to analyze (sub) surface targets in their solid and liquid form. Knowing that ice and brines of Europa are potentially enriched by sulfate and chlorides, this work seeks to evaluate if Raman spectroscopy could be used to semi quantify the saline content of water solutions using space-like instrumentation. To do so, MgSO4 and MgCl2 were used to prepare three sets of water solutions. Raman analyses were then performed by the laboratory simulator of the ExoMars Raman Laser Spectrometer (RLS), which has been defined as the threshold system for the Europa Lander. After data analysis, two different semi-quantification approaches were tested, and their results compared. Although univariate calibration curves proved to successfully quantify the content of SO42− and Cl− anions dissolved in mono-analyte water solutions, this strategy provided very poor results when applied to binary saline mixtures. Overcoming this issue, the non-linearity prediction ability of Artificial Neural Networks (ANNs) in combination with bandfitting allows to successfully resolve the complexity of the vibrational perturbation suffered by the OH region, which is caused by the cross interaction of H2O molecules with different anions., Ministerio de Economía y Competitividad, Grant/Award Number: PID2019-107442RBC31.

With a growing interest on icy worlds and the exploration of the Outer Solar System different proposals for different missions have been considered in the last years. One the most interesting planetary bodies for a lander-kind mission is Europa, thanks to its astrobiological implications. The presence of an underlying liquid ocean, exchanging material with the surface of its ice crust, makes of great interest the use of a lander with capabilities to characterize the possible organics present in this icy world, but also to understand the environment in which those organics could be found. Raman spectroscopy has the unique capability to detect these organics and provide information about the aqueous environment and the different salts in play. In this work we focused in the analyses of different solutions using two different salts, one that can be directly detected in the solution (magnesium sulfate) and other that cannot be directly detected by Raman spectroscopy (magnesium chloride). Despite of not being directly detected, the presence of salts is known to affect the vibrational dynamics of the water, hence, this changes can be observed by Raman spectroscopy, more concisely in the OH vibrations region of its Raman spectrum. Through a process of band fitting to separate the five individual components of this spectral region and adding inputs from the features of the directly observed salt, we have developed a different models to calculate the salinity of different mixtures. Starting with univariate models useful for one component solutions, these models failed, as expected, to calculate the quantity of one of the salts when the other was also present in the solution. Using this band fitting process as dimensional reduction method for our data set, we trained a model using Artificial Neural Networks that successfully could calculate the cuantity of each salt in these binary solutions, and also characterize the ones with just one salt.

The Raman Laser Spectrometer (RLS) is part of the analytical payload located inside Rosalind Franklin rover for the Exomars Mission to Mars. The RLS instrument consists of three main units: 1) the optical head that focus the laser excitation on the sample and collect the scattered light from the same area (with a 50 microns spot); 2) the spectrometer analyzing the Raman signal in the spectral range 150-3800 cm-1 with an average spectral resolution of 8 cm-1 and 3) an electronic control unit in which the laser is included. These units are connected by optical fibers and electrical hardness. The instrument will investigate powdered samples collected by the rover at the surface and subsurface of Mars at the mineral grain scale. (1) The RLS development stages comprised the development, verification, test and evaluation of the scientific performances of two main models: Engineering Qualification Model (EQM) and Flight Model (FM). Because the consecutive delays in Exomars launch to Mars an important aspect related with this situation is the evaluation of the scientific performances with time of these models comparing the results obtained at the pre-delivery stage with those obtained at the rover analytical laboratory drawer (ALD) and rover integrated stages. Additionally it is also of great interest evaluate the scientific results obtained in the framework of dedicated science activities currently ongoing at the ALD and rover levels in which the evaluation of the combined science potential among the three instruments inside Rosalind Franklin rover (MicrOmega, RLS and MOMA) is outstanding. In the present work interest is devoted to the scientific performances evaluation of the RLS-FM at the different levels: pre-delivery, rover analytical drawer (ALD) and finally integrated on the Rosalind Franklin rover. For that, observation of the data obtained on the calibration target (CT) is mainly used although data obtained on standard and natural samples at the pre-delivery stage are also presented and discussed. Instrument response as function of temperature, atmospheric pressure conditions and changes on the main acquisition parameters was evaluated. Estimation of the different band parameters observed (band position, intensity, bandwidth and SNR) allowed performances comparison along the different phases of the process and comparison with the established scientific requirements. References: Rull, S. Maurice, I. Hutchinson, A. Moral et al., Astrobiology, 2017, 17, 627-654.

Producción Científica, The SuperCam and SHERLOC instruments onboard the NASA/Perseverancerover are returning the first Raman spectra to be ever collected from anotherplanet. Similarly, the RLS instrument onboard the ESA/Rosalind Franklinrover will collect Raman spectra from powdered rocks sampled from thesubsurface of Mars. To optimize the scientific exploitation of Raman spectrareturned from planetary exploration missions, tailored chemometric tools arebeing developed that take into account the analytical capability of the men-tioned Raman spectrometers. In this framework, the ERICA research groupis using laboratory simulators of SuperCam and RLS to perform representa-tive laboratory studies that will enhance the scientific outcome of bothMars2020 and ExoMars missions. On one hand, preliminary studies provedthe chemometric analysis of RLS datasets could be used to obtain a reliablesemi-quantitative estimation of the main mineral phases composing Martiangeological samples. On the other hand, it was proved the data fusion ofRaman and LIBS spectra gathered by SuperCam could be used to enhancethe discrimination of mineral phases from remote geological targets. Besidesdescribing the models developed by the ERICA group, this work presents anoverview of the complementary chemometric approaches so far tested in thisfield of study and propose further improvements to be addressed in thefuture., Ministerio de Economía y Competitividad, Beca/Concesión Número:PID2019-107442RBC31, European Union’s Horizon 2020 research and innovation program. grant agreement no. 687302

Producción Científica, The Mars2020/Perseverance and ExoMars/Rosalind Franklin rovers are bothslated to return the first Raman spectra ever collected from another planetarysurface, Mars. In order to optimize the rovers scientific outcome, the scientificcommunity needs to be provided with tailored tools for data treatment andinterpretation. Responding to this need, the purpose of the Analytical Databaseof Martian Minerals (ADaMM) project is to build an extended multianalyticaldatabase of mineral phases that have been detected on Mars or are expected tobe found at the landing sites where the two rovers will operate. Besides the useof conventional spectrometers, the main objective of the ADaMM database isto provide access to data collected by means of laboratory prototypes simulat-ing the analytical performances of the spectroscopic systems onboard the Mars2020 and ExoMars rovers. Planned to be released to the public in 2022,ADaMM will also provide access to data treatment and visualization toolsdeveloped in the framework of the mentioned space exploration missions. Assuch, the present work seeks to provide an overview of the ADaMM onlineplatform, spectral tools, and mineral collection. In addition to that, themanuscript describes the Raman spectrometers used to analyze the mineralcollection and presents a representative example of the analytical performanceensured by the Raman prototypes assembled to simulate the Raman LaserSpectrometer (RLS) and SuperCam systems., European Union’s Horizon 2020 research and innovation program. grant agreement no. 687302., Ministerio de Economía y Competitividad (Grant/Award Number: PID2019-107442RB-C31)

The PTAL Project: Mars2020/Perseverance 1 and ExoMars/Rosalind Franklin 2 rovers will look for traces of present or past life on Mars. To do so, the spectroscopic systems included in their analytical payloads will investigate the geochemistry and mineralogy of Martian rocks and soils to detect geological samples that could potentially host biomarkers. In order to optimize the scientific exploitation of planetary spectroscopic analysis, the PTAL project will provide the scientific community with a novel library of terrestrial analogue materials that have been selected based on their similarity to well-known Martian geological contexts. Funded by the European Union’s Horizon 2020 research and innovation programme under grant agreement Nº 687302, the PTAL online platform will be released to public in October 2021. As further detailed by Werner et al. during this conference, the core of the database are the spectroscopic data collected by means of multiple Raman (University of Valladolid, UVa, Spain), NIR (University of Paris-Sud, UP-Sud, France) and LIBS (French National Centre for Scientific Research, IRAP, France) systems. Spectroscopic results are additionally supported by X-ray diffractograms and thin section observations (University of Oslo, Uio, Norway) to provide an exhaustive geochemical and mineralogical characterization of the samples. The whole set of data, collected by means of both commercial systems and prototypes/flight spares (FS) of analytical instruments validated for Mars exploration (RLS-Sim, MicrOmega-FS, ChemCam-FS), will be available to the public thanks to a dedicated online platform, which main characteristics are detailed below.The online PTAL platform:The PTAL database will be accessible to public through the following URL: http://erica.uva.es/PTAL/. After login (credentials will be provided by the PTAL consortium upon request), future users will have access to the whole set of diffractometric and spectroscopic data collected from a total of 102 analogue materials. On one side, clicking on the sample name, the metadata associated to the selected terrestrial analogues are provided (e.g., Sample Name and Lithology, Sampling Campaign and coordinates) together with high quality pictures of the terrestrial analogue sample. On the other side, by clicking on “analytical summary”, the PTAL platform displays the list of NIR, LIBS, Raman and XRD analyses associated to the selected terrestrial analogue, together with a table summarizing and comparing the main results gathered from each technique (Figure 1).Figure 1: Screenshots collected from the PTAL online database: a) list of samples, b) summary result of a selected analogue, and c) online visualization of a selected Raman spectrum.At this stage, all NIR, XRD, Raman and LIBS data have been successfully uploaded to the PTAL database 3–5. In detail, the PTAL database provides access to 102 diffractograms (1 per sample), 102 LIBS spectra, 102 NIR spectra collected by means of the commercial spectrometer, and 102 NIR data cubes obtained through the MicrOmega system (of them composed of 62500 spectra collected at steps of 20µm in a field of view of 5x5mm). Regarding Raman results, only the spectra providing the highest mineralogical information were uploaded to the PTAL database. As such, the number of Raman spectra was reduced from over 4500 to 577 (an average of 5-6 spectra per sample). 245 of them were collected by means of the RLS-Sim, while the remaining 332 were obtained with a commercial spectrometer. All data can be either visualized online or downloaded for further data comparison and processing. In this framework, it must be underlined the PTAL platform also gives access to a dedicated software for data treatment. Named SpectPro, the details of this downloadable software are detailed below.The SpectPro software:Developed in the framework of the ExoMars mission 6, the PTAL version of the SpectPro software could be downloaded from the PTAL webpage (download section) for both windows and MacOs operating systems. Through the SpectPro software, PTAL users will be able to run individual and multi-spectra operations such as labelling, trimming, shifting, normalization, baseline correction (see Figure 2).Figure 2: Screenshot of PTAL/SpectPro, in which the main functionalities and characteristics of the software are highlighted.Among the main functionalities, the software also features a general-purpose spectrum calculator to perform lineal combinations, product and derivative of spectra, among others. The software team has been working to facilitate a direct access from SpectPro to the PTAL database, using the same credentials for access to the PTAL web interface. This connection will boost the capability of the scientist working in a planetary mission (but not only) to perform a fast and comprehensive characterization and identification of the mineral phases present in a sample by comparing the data obtained from the sample with the extensive spectral information included in the PTAL database. This will be possible by profiting from the navigation pane included in SpectPro. In addition, using the peak detection capabilities of SpectPro, it will be possible to perform sample identification based on the acquired spectra.Acknowledgments: This work is financed through the European Research Council in the H2020- COMPET-2015 programme (grant 687302).References: 1 Farley, K. A. et al. Space Sci. Rev. 216, 142 (2020); 2 Vago, J. L. et al. Astrobiology 17, 471–510 (2017); 3 Lantz, C. et al. Planet. Space Sci. 189, 104989 (2020); 4 Loizeau, D. et al. Planet. Space Sci. 193, 105087 (2020); 5 Veneranda, M. et al. J. Raman Spectrosc. 1–19 (2019) doi:10.1002/jrs.5652; 6 Lopez-Reyes G. et al. European Planetary Science Congress 2018 vol. 12 1–2 (2018).

On the NASA 2020 rover mission to Jezero crater, the remote determination of the texture, mineralogy and chemistry of rocks is essential to quickly and thoroughly characterize an area and to optimize the selection of samples for return to Earth. As part of the Perseverance payload, SuperCam is a suite of five techniques that provide critical and complementary observations via Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), visible and near-infrared spectroscopy (VISIR), high-resolution color imaging (RMI), and acoustic recording (MIC). SuperCam operates at remote distances, primarily 2-7 m, while providing data at sub-mm to mm scales. We report on SuperCam's science objectives in the context of the Mars 2020 mission goals and ways the different techniques can address these questions. The instrument is made up of three separate subsystems: the Mast Unit is designed and built in France; the Body Unit is provided by the United States; the calibration target holder is contributed by Spain, and the targets themselves by the entire science team. This publication focuses on the design, development, and tests of the Mast Unit; companion papers describe the other units. The goal of this work is to provide an understanding of the technical choices made, the constraints that were imposed, and ultimately the validated performance of the flight model as it leaves Earth, and it will serve as the foundation for Mars operations and future processing of the data. In France was provided by the Centre National d'Etudes Spatiales (CNES). Human resources were provided in part by the Centre National de la Recherche Scientifique (CNRS) and universities. Funding was provided in the US by NASA's Mars Exploration Program. Some funding of data analyses at Los Alamos National Laboratory (LANL) was provided by laboratory-directed research and development funds.

In February 2021, NASA’s Perseverance rover will begin its exploration of Jezero crater near a putative ancient delta. Orbital mineralogy indicates the presence of carbonates and clay minerals in the landing site, which will be key targets for study. The SuperCam instrument provides an important tool for remotely surveying for these and other minerals using multiple techniques: Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman (TRR) and Luminescence (TRL) spectroscopies, Visible-Near Infrared (VisIR) spectroscopy, micro-imaging, and acoustics. TRR and TRL use a pulsed 532 nm laser with an adjustable gate width, from 100 ns to several ms. The time at which the gate opens is also adjustable, from coincident with the laser pulse to obtain Raman and fast luminescence out to 10 ms or more to capture the lifetimes of luminescence signals. These techniques will operate at distances up to 7 m from the rover mast and will be most effective if LIBS first removes dust from the targets and chemistry is subsequently obtained at the same location. Early lab results show that TRR is effective for detecting certain carbonates (magnesite, hydromagnesite, siderite, ankerite, calcite, and dolomite), sulfates (gypsum, anhydrite, barite, epsomite, and coquimbite), phosphates (apatite), and silicates (e.g., quartz, feldspar, forsteritic olivine, topaz, and diopside). Many of these minerals are high-priority targets for astrobiology studies because they represent habitable environments and have high biosignature preservation potential in terrestrial rocks. Raman signal strength is significantly decreased in fine-grained materials, however, and clay minerals will be a challenge to detect, as will opaque minerals such as Fe-oxides. TRL will be useful for identifying rare earth elements in phosphates and zircon, Fe3+ in silicates such as feldspar, Mn2+ in carbonates, and Cr3+ in Al-oxides and some silicates. TRL may also be able to identify fast (

NASA/Mars2020 and ESA/ExoMars missions will look for traces of present or past life on Mars. To do so, both Perseverance and Rosalind Franklin rovers have been equipped with a wide set of spectroscopic systems to investigate the geochemistry and mineralogy of Martian rocks and soils. As spectroscopic techniques are acquiring an increasing importance in the field of Mars exploration, many research groups are trying to estimate and optimize their potential scientific return by carrying out representative analytical studies in the laboratory.In this framework, PTAL is a research project founded by the European Commission through the H2020 program, which is aimed to provide the scientific community with a novel library of terrestrial analogue materials that have been selected based on their similarity to well-known Martian geological contexts. Planned to be released to public on January 2022, the PTAL platform (http://erica.uva.es/PTAL/) will provide future users with access to complementary spectroscopic and diffractometric data gathered from over 100 terrestrial analogues.In detail, the XRD analysis of each analogue was carried out to gather a reliable overview of samples mineralogy. Then, LIBS, IR and Raman spectrometers were used to collect additional elemental and molecular data, these being the key analytical tools onboard NASA/Perseverance and ESA/Rosalind Franklin rovers. Beside the use of commercial spectrometers, the RLS ExoMars Simulator, the MicrOmega-Flight (FS) (Spare Model) and the ChemCam-FS were also employed to collect LIBS, Raman and NIR spectra (respectively) qualitatively comparable to those that will soon gathered on Mars.In addition to analytical data, the PTAL platform will also provide direct access to a dedicated software (SpectPro) for spectral visualization and treatment [1]To conclude, future users can also request physical access to the terrestrial analogues, so that the data contained in the PTAL library can be combined with further analysis in the laboratory.To obtain further information about the PTAL project, please use the QR code provided in Figure 01.Figure 01: PTAL QR codeAcknowledgements: This work is financed through the European Research Council in the H2020- COMPET-2015 programme (grant 687302) and the Ministry of Economy and Competitiveness (MINECO, grant PID2019-107442RB-C31).References: [1] Saiz J. et al., (2019) EGU general Assembly, 21, 17904.

The SuperCam instrument suite provides the Mars 2020 rover, Perseverance, with a number of versatile remote-sensing techniques that can be used at long distance as well as within the robotic-arm workspace. These include laser-induced breakdown spectroscopy (LIBS), remote time-resolved Raman and luminescence spectroscopies, and visible and infrared (VISIR; separately referred to as VIS and IR) reflectance spectroscopy. A remote micro-imager (RMI) provides high-resolution color context imaging, and a microphone can be used as a stand-alone tool for environmental studies or to determine physical properties of rocks and soils from shock waves of laser-produced plasmas. SuperCam is built in three parts: The mast unit (MU), consisting of the laser, telescope, RMI, IR spectrometer, and associated electronics, is described in a companion paper. The on-board calibration targets are described in another companion paper. Here we describe SuperCam's body unit (BU) and testing of the integrated instrument. The BU, mounted inside the rover body, receives light from the MU via a 5.8 m optical fiber. The light is split into three wavelength bands by a demultiplexer, and is routed via fiber bundles to three optical spectrometers, two of which (UV and violet; 245-340 and 385-465 nm) are crossed Czerny-Turner reflection spectrometers, nearly identical to their counterparts on ChemCam. The third is a high-efficiency transmission spectrometer containing an optical intensifier capable of gating exposures to 100 ns or longer, with variable delay times relative to the laser pulse. This spectrometer covers 535-853 nm ( 105 - 7070 cm − 1 Raman shift relative to the 532 nm green laser beam) with 12 cm − 1 full-width at half-maximum peak resolution in the Raman fingerprint region. The BU electronics boards interface with the rover and control the instrument, returning data to the rover. Thermal systems maintain a warm temperature during cruise to Mars to avoid contamination on the optics, and cool the detectors during operations on Mars. Results obtained with the integrated instrument demonstrate its capabilities for LIBS, for which a library of 332 standards was developed. Examples of Raman and VISIR spectroscopy are shown, demonstrating clear mineral identification with both techniques. Luminescence spectra demonstrate the utility of having both spectral and temporal dimensions. Finally, RMI and microphone tests on the rover demonstrate the capabilities of these subsystems as well., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

We evaluated the effectiveness of the ExoMars Raman laser spectrometer (RLS) to determine the degree of serpentinization of olivine-rich units on Mars. We selected terrestrial analogs of martian ultramafic rocks from the Leka Ophiolite Complex (LOC) and analyzed them with both laboratory and flight-like analytical instruments. We first studied the mineralogical composition of the samples (mostly olivine and serpentine) with state-of-the-art diffractometric (X-ray diffractometry [XRD]) and spectroscopic (Raman, near-infrared spectroscopy [NIR]) laboratory systems. We compared these results with those obtained using our RLS ExoMars Simulator. Our work shows that the RLS ExoMars Simulator successfully identified all major phases. Moreover, when emulating the automatic operating mode of the flight instrument, the RLS ExoMars Simulator also detected several minor compounds (pyroxene and brucite), some of which were not observed by NIR and XRD (e.g., calcite). Thereafter, we produced RLS-dedicated calibration curves (R2 between 0.9993 and 0.9995 with an uncertainty between ±3.0% and ±5.2% with a confidence interval of 95%) to estimate the relative content of olivine and serpentine in the samples. Our results show that RLS can be very effective in identifying serpentine, a scientific target of primary importance for the potential detection of biosignatures on Mars—the main objective of the ExoMars rover mission., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

In this work, the analytical research performed by the Raman Laser Spectrometer (RLS) team during the ExoFiT trial is presented. During this test, an emulator of the Rosalind Franklin rover was remotely operated at the Atacama Desert in a Mars-like sequence of scientific operations that ended with the collection and the analysis of two drilled cores. The in-situ Raman characterization of the samples was performed through a portable technology demonstrator of RLS (RAD1 system). The results were later complemented in the laboratory using a bench top RLS operation simulator and a X-Ray diffractometer (XRD). By simulating the operational and analytical constraints of the ExoMars mission, the two RLS representative instruments effectively disclosed the mineralogical composition of the drilled cores (k-feldspar, plagioclase, quartz, muscovite and rutile as main components), reaching the detection of minor phases (e.g., additional phyllosilicate and calcite) whose concentration was below the detection limit of XRD. Furthermore, Raman systems detected many organic functional groups (–C≡N, –NH2 and C–(NO2)), suggesting the presence of nitrogen-fixing microorganisms in the samples. The Raman detection of organic material in the subsurface of a Martian analogue site presenting representative environmental conditions (high UV radiation, extreme aridity), supports the idea that the RLS could play a key role in the fulfilment of the ExoMars main mission objective: to search for signs of life on Mars. This work is financed through the European Research Council in the H2020-COMPET-2015 programme (Grant 687302) and the Ministry of Economy and Competitiveness (MINECO, Grants ESP2017-87690-C3-1-R and PID2019-107442RB-C31). The authors would also like recognize the support of the European Space Agency (ESA) and are grateful to all ExoMars team members participating in the ExoFiT trial. Peerreview

Producción Científica, The Raman laser spectrometer (RLS) instrument onboard the Rosalind Franklin rover of the ExoMars 2022 mission will analyze powdered samples on Mars to search for traces of life. To prepare for the mission, the RLS scientific team has developed the RLS ExoMars Simulator (RLS Sim), a flexible model of RLS that operates similarly to the actual instrument, both in laboratory and field conditions, while also emulating the rover operational constraints in terms of sample distribution that are relevant to the Raman analysis. This system can operate autonomously to perform RLS-representative analysis in one or several samples, making it very useful to perform heavy experimental tasks that would otherwise be impossible using a flight-representative model of the instrument. In this work, we introduce the current configuration of the RLS Sim that has incorporated new hardware elements such as the RAman Demonstrator 1 (RAD1) spectrometer with the objective of approaching its performance to that of the actual RLS instrument. To evaluate the scientific capability of the RLS Sim, we have compared it with a replica model of RLS, the RLS Flight Spare (FS). Several acquisition aspects have been evaluated based on the analysis of select samples, assessing the performance in terms of spectral range and resolution and also studying several issues related to the evolution of signal-to-noise ratio (SNR) with different acquisition parameters, especially the number of accumulations. This performance analysis has shown that the RLS Sim in its updated configuration will be a key model to perform support science for the ExoMars mission and the RLS instrument on the Rosalind Franklin rover. Designed to work intensively, the use of the RLS Sim in combination with the RLS FS will facilitate maximizing the scientific return of the RLS spectrometer during Martian operations., Secretaría de Estado de Investigación, Desarrollo e Innovación (grant PID2019-107442RBC31), European Union’s Horizon 2020 research and innovation program (grant 687302)

Producción Científica, The 2020s could be called, with little doubt, the "Mars decade". No other period in space exploration history has experienced such interest in placing orbiters, rovers and landers on the Red Planet. In 2021 alone, the Emirates' first Mars Mission (the Hope orbiter), the Chinese Tianwen-1 mission (orbiter, lander and rover), and NASA's Mars 2020 Perseverance rover reached Mars. The ExoMars mission Rosalind Franklin rover is scheduled for launch in 2022. Beyond that, several other missions are proposed or under development. Among these, MMX to Phobos and the very important Mars Sample Return can be cited. One of the key mission objectives of the Mars 2020 and ExoMars 2022 missions is the detection of traces of potential past or present life. This detection relies to a great extent on the analytical results provided by complementary spectroscopic techniques. The development of these novel instruments has been carried out in step with the analytical study of terrestrial analogue sites and materials, which serve to test the scientific capabilities of spectroscopic prototypes while providing crucial information to better understand the geological processes that could have occurred on Mars. Being directly involved in the development of three of the first Raman spectrometers to be validated for space exploration missions (Mars 2020/SuperCam, ExoMars/RLS and RAX/MMX), the present review summarizes some of the most relevant spectroscopy-based analyses of terrestrial analogues carried out over the past two decades. Therefore, the present work describes the analytical results gathered from the study of some of the most distinctive terrestrial analogues of Martian geological contexts, as well as the lessons learned mainly from ExoMars mission simulations conducted at representative analogue sites. Learning from the experience gained in the described studies, a general overview of the scientific outcome expected from the spectroscopic system developed for current and forthcoming planetary missions is provided., Ministerio de Economía, Industria y Competitividad (grants PID2019-107442RB-C31 and RDE2018-102600-T), Consejo Europeo de Investigación (grant 687302)

IntroductionThe flight Raman instrument for the ExoMars 2022 mission, the Raman Laser Spectrometer (RLS) [1], was delivered and integrated in the Rosalind Franklin rover. In parallel, the RLS flight spare (FS) model is being used at INTA facilities to thoroughly characterize and understand the instrument performance, as well as to optimize the scientific return of the flight instrument through a proper parameterization. In addition, the RLS ExoMars simulator developed by the University of Valladolid (UVA), is used for thorough analysis of samples, emulating the operation mode of the RLS instrument (including the automated adaptation to the sample spot), as well as the sample preparation and distribution system (SPDS) of the rover, in those aspects related to sample management.In this work we present experiments and analysis performed with the different ground models, aimed at the optimization and characterization of the RLS performance, by addressing the following three issues: 1- optimizing the acquisition by studying the SNR of spectra with different configurations of the spectra acquisition algorithms implemented onboard the RLS instrument [2] (especially the number of accumulations), while also considering the influence of the instrument stability (laser power, CCD temperature, etc.). 2- optimizing the spectral quality of the acquired data by evaluating several on-ground spectral data-processing strategies. 3- evaluate and analyze the performance of the different models (FM, FS and Simulator) to understand the expected inter-correlation of the results obtained with them.Experiments and previous workSeveral samples with different emission efficiencies (diamond, calcite, serpentine, hematite and vermiculite), have been analyzed with the RLS FS and the RLS ExoMars Simulator, acquiring a relatively high number of acquisitions. The data has been processed to establish the spectral quality (measured as the SNR) as a function of the number of accumulations.The RLS ExoMars simulator, on the other hand, has also been reworked to integrate the RAD1 spectrometer (RAman Demonstrator 1, a laboratory model with characteristics and design similar to RLS). This will bring the RLS ExoMars Simulator closer to the expected performance of the instrument that will fly to Mars.Optimal naThe RLS instrument features an automated integration time (ti) calculation algorithm, which allows optimizing this time for every spot in the sample. However, due to several reasons, the number of accumulations (na) has to be established from ground as a system parameter, so it will be the same for all the samples and spots obtained during one operational cycle (sol). It has been reported [2] that, for constant total acquisition times (ti*na) in instruments such as RLS, the signal to noise ratio (SNR) of a spectrum increases more by maximizing ti, than by maximizing na. This is in agreement with the implementation performed on the onboard software of RLS. Thus, the present study is centered in the characterization of the optimal number of accumulations (which is configurable from ground) for the RLS operation.The results in this work have been used to infer the SNR evolution of the spectra as a function of the number of accumulations, which is critical to establish the on-ground parameter for na for an optimal acquisition. The results are obtained by comparing several SNR calculation methods, and have helped determining a good compromise in the selection of the na at a value of 30.This analysis has shown noise levels behaving very close to the theoretical behavior, with the noise intensity following the expected inverse exponential decay with na. However, it has also provided insight as to how the spectra peak intensity is highly affected by the laser power or CCD temperature stability. In this sense it has been concluded that it will be necessary to perform some tests at arrival on Mars, in temperature conditions representative of the environment during Martian operations.Data processing for optimal spectral qualityThe analysis of the acquired data has also shown how the spectral quality of the spectra can be influenced by the data processing: CCD binning method, dark subtraction, baseline correction approach… but also how different intensity correction methods can help improve the quality of the spectra. For example, the correction with BZn [3] has been used to perform correction of the spectra (using different correction methods), showing how the data analysis strategy incorporated into the science processing pipelines of RLS during operation will need to include this correction. Other data processing strategies to be considered are the use of optimized binning methods (adjusted for each spectrum), or the dark correction of spectra, which also improves the spectral quality.Correlation between instrument modelsTo have ground models which can be correlated with the instrument on Mars is critical for analysis during operations, but also to prepare and validate the science that will be obtained from the instrument once on Mars. The RLS FS instrument is identical to the flight instrument in every sense, which makes it very representative of the RLS FM, except in the operational conditions, as it is not possible to simulate the Martian conditions in a daily operational basis (and, for example, the CCD working temperature is kept at values higher than what will be expected on Mars).On the other hand, the correlation of ground emulators such as the RLS ExoMars Simulator is of paramount importance to obtain results that are realistically correlated with the actual RLS instrument. The integration of the RAD1 spectrometer in the RLS ExoMars Simulator is a great step forward to achieve representative results that can ultimately be used to take decisions as to how to parameterize the flight instrument for Martian operation.AcknowledgementsMINECO grants ESP2014-56138-C3-1-R, ESP2014-56138-C3-2-R, ESP2107-87690-C3-1-R, ESP2107-87690-C3-3-R.References[1] Rull, F. et al. Astrobiology 17, 627–654 (2017).[2] Lopez-Reyes, G. et al. J. Raman Spectrosc. 48, (2017).[3] A. Sanz-Arranz et al. J. Raman Spectrosc. 48, (2017).

IntroductionThe Raman Laser Spectrometer (RLS) [1] is part of the analytical instrumental suite (Pasteur Payload) located inside the Analytical Laboratory Drawer (ALD) of the Rosalind Franklin rover for the ExoMars 2022 mission to Mars. RLS is based on the inelastic scattering of the matter when illuminated by a monochromatic light. This emitting radiation contains physicochemical information of the observed material through the vibrations of its atomic components. It this way RLS will contribute to the ExoMars scientific mission objectives identifying minerals and organic compounds at the mineral grain scale. And with this information supporting the key astrobiological questions the mission will address analyzing samples on the Martian surface and subsurface.The instrument consists in four main units which are depicted in Figure 1 and its development and delivered models are described in references [1–5].In this work interest is mainly devoted to the analysis of the scientific performances of the flight model (FM) currently integrated in the Rosalind Franklin rover, comparing it with the performances of the flight spare (FS) located at INTA in Madrid. This comparison is part of the general plan to characterize both instruments to better understand the FM behavior in support to the future operation in Mars. This plan also includes the correlation of the FS scientific outcome and the RLS ExoMars Simulator, a laboratory setup located in Valladolid University [6] emulating the RLS acquisition algorithms [7], as well as the sample preparation and distribution system (SPDS) positioning of the samples. Figure 1. RLS instrument units. a) The SPU is the Spectrometer Unit, with a theoretical spectral resolution of 6-8 cm-1 [5]. b) The internal Optical Head (iOH) features an autofocus system, with 50 microns collection and excitation fibers [2,8]. c) The ICEU is the control electronics unit, also integrating the redundant 532 nm excitation laser [9]. d) The Calibration Targets will allow the calibration of the instrument, as well as the spatial correlation of the field-of-views of the different instruments of the Rosalind Franklin Analytical Laboratory Drawer [3].ExperimentalThe instrument performances were evaluated after an appropriate calibration procedure that included observation of Ne and Ar-Hg emission lines to obtain the correlation function between pixels and correct wavelengths and the Raman observation of standard samples and the PET calibration target to obtain the right wavenumber positions.After that a campaign with selected samples of very different Raman molar efficiency was undertaken. In the FM case this campaign comprised the pre-delivery experiments with a limited set of samples, given the extremely tight delivery schedule for the flight instrument to ESA. Once after integration, only the Calibration Target material (PET) can be used for health or any other checks, as no samples will be introduced into the sealed ultra-clean zone of the analytical laboratory drawer (ALD) of the rover until arrival to Mars. However, the development of the RLS FS (identical in every sense to the FM), has provided a unique opportunity to perform thorough scientific analysis that will be used to properly characterize and parameterize the flight instrument. These experiments will be correlated with heavy duty analysis performed by the RLS ExoMars Simulator, which is designed to work in a laboratory environment, thus allowing the analysis of samples without the operational constraints of the RLS FS. Several samples relevant to Mars have been analyzed at the present. These samples are collected from the ADAMM database, a collection of materials representative of different Martian locations and specifically the landing sites of ExoMars 2022 (Oxia Planum) and Mars 2020 (Jezero Crater) missions, which is presented in this conference. In addition, synthetic mixtures of materials used to perform calibration curves for the quantification of mineral abundances from RLS data (publication in press), or other representative materials to optimize the acquisition parameters of the instrument are analyzed (a dedicated presentation is presented in this conference).Results and discussion In this conference we will present and discuss the evolution of Raman spectra of the CT acquired with the RLS FM instrument, to verify the evolution of the instrument throughout all the steps from the pre-delivery stage, including the spectra obtained in relevant environments during the Assembly, Integration and Test (AIT) phases of the ALD and rover integration process. And also, the results regarding the correlation of the FS instrument and the RLS ExoMars Simulator data to the RLS FM instrument. These results will be key for defining the instrument capabilities and expected scientific performance of the instrument once on Mars. AcknowledgementsMINECO grants ESP2014-56138-C3-1-R, ESP2014-56138-C3-2-R, ESP2107-87690-C3-1-R, ESP2107-87690-C3-3-R.References[1] F. Rull et al., et al. Astrobiology. 17 (2017) 627–654. https://doi.org/10.1089/ast.2016.1567.[2] A. Santiago et al. Proc. SPIE - Int. Soc. Opt. Eng., 2018. https://doi.org/10.1117/12.2313462.[3] G. Lopez‐Reyes et al. J. Raman Spectrosc. (2020) jrs.5832. https://doi.org/10.1002/jrs.5832.[4] A.G. Moral et al. J. Raman Spectrosc. (2019) jrs.5711. https://doi.org/10.1002/jrs.5711.[5] J.F. Cabrero et al. In: Proc. SPIE 11180 (2019) 115. https://doi.org/10.1117/12.2536035. [6] G. Lopez-Reyes et al. Eur. J. Mineral. 25 (2013) 721–733. https://doi.org/10.1127/0935-1221/2013/0025-2317.[7] G. Lopez-Reyes, F. Rull Pérez, J. Raman Spectrosc. 48 (2017) 1654–1664. https://doi.org/10.1002/jrs.5185.[8] G. Ramos et al. In: Proc. SPIE - Int. Soc. Opt. Eng., (2017). https://doi.org/10.1117/12.2277003.[9] P. Ribes-Pleguezuelo et al. Proc SPIE - Opt. Eng. 55(11), 116107 (2016), https://doi: 10.1117/1.OE.55.11.116107

NASA/Mars 2020 [1] and ESA/ExoMars [2] missions are scheduled to be launched in 2020 and 2022 respectively. For the first time in history, the analytical payload of both exploration rovers will be equipped with Raman systems that will work in combination with complementary spectroscopic techniques such as LIBS and NIR. Prior to science operations, detailed laboratory investigations are necessary to constrain the potential scientific outcome of Raman spectrometers, as well as to facilitate the comprehension of the advantages provided by combined Raman/LIBS (e.g. the SuperCam analytical suite [3] onboard the Perseverance rover) and Raman/NIR (as is the case of ExoMars RLS [4] and MicrOmega coordinated studies) analysis.In this framework, beside coordinating the development of Mars 2020/SuperCam Calibration Target (SCCT) and ExoMars/Raman Laser Spectrometer (RLS), the ERICA research group is developing novel tools that are meant to facilitate both science operation teams in the analysis and interpretation of the spectroscopic data soon gathered from Mars. As such, the three main tools under development are presented below:1) Planetary Terrestrial Analogue Library (PTAL) Funded by the European Research Council through the H2020-Compet-2015 programme (grant 687302), the Planetary terrestrial analogue library (PTAL) project will provide science operation teams (and, in a broader extent, the whole scientific community) with free access to an extended multi spectral database of terrestrial analogues materials that have been selected basing on their congruence to well-known Martian geological and environmental contexts [5]. Through the collaboration of the Universities of Valladolid (UVa, Spain), Oslo (UiO, Norway) and Paris-Sud (UPSud, France) the PTAL database will offer Raman, LIBS, NIR and XRD data collected from 1) natural geological samples collected from terrestrial analogues sites and 2) artificial samples replicating Martian protoliths composition and altered in the laboratory under controlled physical-chemical conditions. Beside the use of conventional laboratory instruments, the mineralogical and geochemical composition of PTAL samples is characterized by means of spacecraft derived instrumentation, as is the case of the RLS ExoMars Simulator, MicrOmega and ChemCam spare models. Furthermore, the PTAL platform will provide the opportunity to request physical access to Martian analogue materials thus enabling future users to combine PTAL spectroscopic data with further laboratory analysis.2) Analytical DAtabase of Martian Minerals (ADAMM) Complementary to PTAL, the ADAMM database will include diffractometric (XRD) and spectroscopic (Raman, NIR, LIBS) data from a wide collection of pure mineral phases that have been detected on Mars by orbital and on-ground analytical systems, as well as from the laboratory study of Martian meteorites. Financed by the Ministry of Economy and Competitiveness (MINECO, grant ESP2017-87690-C3-1-R) the ADAMM database also includes additional phases that, according to the modern knowledge about the geological evolution of Mars, are most likely to be present at the (sub)surface of the red planet. As such, over 300 specimens are being analyzed using both commercial and spacecraft derived instrumentations. Besides the previously mentioned RLS ExoMars Simulator, mineral samples will be also analyzed by means of SimulCam, a remote Raman/LIBS system recently developed by the ERICA research group to reliably simulate SuperCam analytical outcomes. After comparing ADAMM database with the mineralogy detected from orbit at Jezero Crater and Oxia Planum (the landing site for Mars 2020 and ExoMars missions, respectively) a more detailed analysis of selected samples will be carried out. Thus, complementary analysis will be performed in the framework of the SIGUE-Mars consortium by using additional instruments (including the RLS spare model), and under Martian conditions (temperature and atmospheric pressure). In this way, a reliable estimation of the potential scientific outcome of the forthcoming rover missions to Mars will be provided.3) IDAT/SpectPro The Instrument Data Analysis Tool (IDAT)/SpectPro software was developed by the University of Valladolid to receive, decodify, calibrate and verify the telemetries generated by the RLS instrument on Mars [6]. IDAT/SpectPro is able to open and process data in PDS4 format, as required by the ExoMars mission. In this way, as soon as the data from the processors is available, IDAT/SpectPro will automatically process it to obtain science and engineering (housekeeping) calibrated data and even generate autolooks.IDAT/SpectPro also provides access to an extended set of analytical tools for spectral analysis such as labelling, trimming, shifting, normalization, baseline correction, and features a general-purpose spectrum calculator to perform lineal combinations, product, division and derivative of spectra. An automated identification algorithm to classify Raman spectra is also under development. This algorithm is based on the comparison of peak positions and intensities, which has provided good results, even for the detection of all samples present in simple mixtures.The mentioned analytical tools will be made available to PTAL and ADAMM users through a dedicated version of IDAT/SPectPro software, which will have a direct interface to access the two databases.Acknowledgements:This work is financed through the European Research Council in the H2020- COMPET-2015 programme (grant 687302) and the Ministry of Economy and Competitiveness (MINECO, grant ESP2017-87690-C3-1-R). The authors gratefully acknowledge the support of the SIGUE-Mars consortium (MINECO, grant RDE2018-102600-T). References:[1] Williford, K. H. et al. From Habitability to Life on Mars (Elsevier Inc., 2018). [2] Vago, J. L. et al. Astrobiology 17, 471–510 (2017). [3] Wiens, R. C., Maurice, S. & Perez, F. R. Spectrosc. (Santa Monica) 32, 50–55 (2017). [4] Rull, F. et al. Astrobiology 17, 627–654 (2017). [5] Veneranda, M. et al. J. Raman Spectrosc. 50, 1–19 (2019). [6] Lopez-Reyes G. et al. European Planetary Science Congress 2018 12 1–2 (2018).

Raman Spectroscopy is an analytical technique that will be deployed on Mars in the following years and could be part of other payloads for planetary exploration missions in the future. Its ability for identification of mineral phases and its interest in Mars has been deeply discussed in bibliography [1]. Perseverance rover, to be launched in 2020, and ExoMars rover, to be launched in 2022, will carry three Raman instruments, different in concept and capabilities. SHERLOC (mounted on Perseverance’s arm) is a UV Raman instrument mainly focused in the direct detection of biomarkers, SuperCam (mounted on Perseverance’s mast) is a standoff, multi-technique, instrument that performs Raman and LIBS at distances of several meters from the rover. Finally, RLS, mounted in Rosalind Franklin Rover, in the Pasteur analytical laboratory, is a continuous wave, 532 nm excitation source Raman instrument. While the first one is focused in detection limits of organics, RLS is intended to investigate mineralogy and possible biomarkers, while SuperCam, due to its standoff and time resolved design, is a different concept to que other two Raman instruments, as it is also capable of fusing data from different techniques. Carbonates are minerals of great interest for astrobiology, and, as suggested by CRISM data, the landing site selected for the NASA/Mars 2020 rover mission (Jezero crater) presents a variety of Fe-Ca-Mg carbonate units [2]. For Oxia Planum, Rosalind Franklin’s landing site, although no carbonates have been detected in that area by orbiter data, Earth analogues suggest that small amounts of carbonates might be found in the clay rich area. On Earth, top bench Raman spectrometers can be effectively used to discriminate carbonates and to determine the Mg/Fe concentration ratio of mineral species from dolomite (CaMg(CO3)2) - ankerite (CaFe(CO3)2) and magnesite (MgCO3) - siderite (FeCO3) solid solutions series [3]. The previously mentioned instruments might present limitations derived from the design constrains of space exploration. Resolution, far from ideal, and low intensity of the signal, are two of the main factors that could affect the possible calculations done with data from the three Raman instruments. SuperCam is a special case, as it is able to obtain data from several techniques from the same spot of the sample, and that might help to overcome those difficulties. In this work a complete set of Ca-Mg-Fe carbonates is analysed by different Raman instruments, including automated contact instruments and combined standoff developments. The initial characterization of the samples is done with XRD, as gold standard. Then, a characterization of all those carbonates based only on Raman data sets was done, aiming to evaluate the impact of resolution in the classification power of Raman-based calculations. A detailed vibrational mode analysis was carried out for interpreting the structural modifications induced by cationic substitution. Here, after a detailed interpretation it was found that Raman active internal modes are less sensitive to the carbonate chemistry than the external modes (i.e. the 155cm-1 and 286cm-1 respectively). Same collection of carbonates is analysed using standoff Raman-LIBS combination. In this case we will evaluate how having the complementary information of the elemental composition improves the results obtained by standoff Raman spectroscopy [4], as LIBS is more sensitive to the possible changes in the cations in the samples. Using these data sets, a combination of univariate and multivariate calculations are done to evaluate their classification capacity. As commented before, LIBS can classify better these minerals thanks to its lower detection limit and a better functionality in standoff configuration. However, the effect from other phases, different from carbonates, might disturb the LIBS calculations, reason why having an assessment of all the phases in play by Raman spectroscopy is of great interest, supporting the idea of the power of technique combination. 1 F. Rull, S. Maurice, I. Hutchinson et al. Astrobiology, Vol. 17 (2017), No. 6-7 2 B.H.N. Horgan, R.B. Anderson, G. Dromart, E.S. Amador, M.S. Rice Icarus, 339 (2020) 113526. 3 P. Kristova, L. Hopkinson, K. Rutt, H. Hunter, G. Cressey, American Mineralogist, 98 (2013) 401-409. 4 J.A. Manrique-Martinez et al. Journal of Raman Spectroscopy (2020) 1-16.

SuperCam is a highly integrated remote-sensing instrumental suite for NASA’s Mars 2020 mission. It consists of a co-aligned combination of Laser-Induced Breakdown Spectroscopy (LIBS), Time-Resolved Raman and Luminescence (TRR/L), Visible and In frared Spectroscopy (VISIR), together with sound recording (MIC) and high-magnification imaging techniques (RMI). They provide information on the mineralogy, geochemistry and mineral context around the Perseverance Rover. The calibration of this complex suite is a major challenge. Not only does each technique require its own standards or references, their combination also introduces new requirements to obtain optimal scientific output. Elemental composition, molecular vibrational features, fluorescence, morphology and texture provide a full picture of the sample with spectral information that needs to be co-aligned, correlated, and individually calibrated. The resulting hardware includes different kinds of targets, each one covering different needs of the instrument. Standards for imaging calibration, geological samples for mineral identification and chemometric calculations or spectral references to calibrate and eval uate the health of the instrument, are all included in the SuperCam Calibration Target (SCCT). The system also includes a specifically designed assembly in which the samples are mounted. This hardware allows the targets to survive the harsh environmental condi tions of the launch, cruise, landing and operation on Mars during the whole mission. Here we summarize the design, development, integration, verification and functional testing of the SCCT. This work includes some key results obtained to verify the scientific outcome of the SuperCam system., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

As part of the ESA ExoMars rover payload, the Raman Laser Spectrometer (RLS) is scheduled to deploy on Mars in 2021. Together with MicrOmega (NIR) and MOMA (GC-MS), the instrument will analyze Martian subsoil samples to determine their mineralogical composition and investigate the potential presence of biomarkers. Beside the challenges associated with the development of the first Raman spectrometer to be validated for planetary exploration (together with Mars2020/ Sherloc and Supercam systems), to optimize the scientific outcome of RLS spectra gathered on Mars has a crucial importance in the fulfillment of the mission aims. Thus, the RLS team is developing tailored chemometric tools that, taking into account technical specifications and the operational mode of the RLS system, could be used to semi-quantify the main phases composing Martian samples.Considering that 1) the serpentinization of olivine-bearing rocks on Earth plays a key role in the proliferation of microorganisms and in the preservation of biomarkers, and 2) remote sensing systems (e.g. CRISM) detected vast serpentine-bearing deposits on Mars, the present work seek to provide the chemometric tools necessary to correctly define the serpentinization degree of Martian rock samples through the interpretation of RLS data.To do so, olivine and serpentine certified materials were mixed at different concentration ratios and 39 spot of analysis por sample were analyzed by means of the RLS ExoMars Simulator. Data sets were then analyzed using uni-variate (intensity ratio between olivine and serpentine main peaks) and multi-variate (a combination of principal component analysis and artificial neural networks PCA-ANN) methods.The two uni-variate and multi-variate semi-quantification models were finally applied to the study of serpentinized rocks sampled from the Leka Ophiolite Complex (LOC), being those part of the Planetary Terrestrial Analogue Library (PTAL) collection. RLS-based semi-quantification results were finally compared to those obtained from the use of a state-of-the-art laboratory X-ray diffractometer (XRD).Our study suggest that the uni-variate method provide excellent results when the analyzed rocks are mainly composed of olivine and serpentine. However, the estimation reliability decreases when the mineralogical heterogeneity of the sample increases (Raman features of additional mineral phase may overlap the selected olivine and serpentine peaks). In these cases, the multi-variate method based on the combination of PCA and ANN helps to more accurate estimate the serpentinization degree of the terrestrial analogs.In conclusion, the preliminary results summarized in this work indicates that the study of terrestrial analogs is of crucial importance to test and validate RLS-dedicated semi-quantification models. In a broader perspective, it also highlights the importance of developing multiple chemometric tools, since the effectiveness of each of them varies according to mineralogical complexity of the sample under study.

The ESA/Roscosmos ExoMars mission to Mars is scheduled to be launched in 2020. Seeking to prepare the ExoMars operation team to manage the engineering and scientific challenges arising from the Rosalind Franklin rover soon operating at Oxia Planum, a rover prototype equipped with representative ExoMars navigation and analytical systems was recently used in two mission simulations (ExoFit trials)The first field test was carried out in Tabernas (Spain), a desertic area characterized by the presence of clays, partially altered sedimentary rocks and efflorescence salts. The second ExoFit trial was performed in the Atacama Desert (Chile), in a sandy flat land displaying diorite-boulders, clays patches and evaporites.The Raman Laser Simulator (RLS) team participated in both simulations: portable spectrometers were used to determine the mineralogical composition of subsoil samples collected by the rover-drill and to investigate the possible presence of biomarkers. In-situ analysis were carried out by means of the RAD 1 system (Raman Demonstrator), which is a portable spectrometer that follows the same geometrical concept and spectral characteristics of the RLS flight model (FM).In the case of Tabernas trial, additional analysis were performed using the RLS qualification model (EQM2) which at the moment was the most reliable tool to understand the scientific outcome that could derive from the RLS operating on Mars.Prior to analysis, geological samples were crushed and sieved to replicate the granulometry of the powdered material produced by the ExoMars crusher. After flattening, from 8 to 10 spots were analyzed and Raman data and interpreted.From each site, two cores were drilled and analyzed. On one side, the main mineralogical phases detected in the first Atacama core are quartz and calcium carbonate. In addition to those, the mineralogy of the second core also includes hematite and calcium sulphate.On the other side, RAD 1 spectra gathered from Almeria core-samples confirmed the presence of quartz as main mineralogical phase. However, peaks of medium intensity at 146 and 1086 cm-1 were also observed, confirming the detection of rutile and calcium carbonate respectively. The same samples were further characterized by means of the RLS-EQM2 system: beside confirming the detection of the abovementioned mineral phases, additional Raman biomarkers-related peaks were also found.Even though deeper Raman analysis of ExoFit samples need to be performed, the preliminary results gathered in-situ suggests that Raman spectroscopy could play a kay role in the fulfillment of the ExoMars mission objectives.

The ExoMars rover, scheduled to be launched in 2020, will be equipped with a novel and diverse payload. It will also include a drill to collect subsurface samples (from 0- to 2-m depth) and deliver them to the rover analytical laboratory, where it will be possible to perform combined science between instruments. For the first time, the exact same sample target areas will be investigated using complementary analytical methods—infrared spectrometry, Raman spectrometry, and laser desorption mass spectrometry—to establish mineralogical and organic chemistry composition. Fundamental for implementing this cooperative science strategy is the Raman Laser Spectrometer (RLS) calibration target (CT). The RLS CT features a polyethylene terephthalate disk used for RLS calibration and verification of the instrument during the mission. In addition, special patterns have been recorded on the RLS CT disk that the other instruments can detect and employ to determine their relative position. In this manner, the RLS CT ensures the spatial correlation between the three analytical laboratory instruments: MicrOmega, RLS, and MOMA. The RLS CT has been subjected to a series of tests to qualify it for space utilization and to characterize its behavior during the mission. The results from the joint work performed by the RLS and MicrOmega instrument teams confirm the feasibility of the “combined science” approach envisioned for ExoMars rover operations, whose science return is optimized when complementing the RLS and MicrOmega joint analysis with the autonomous RLS operation., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737); Spanish Ministerio de Economía y Competitividad (MINECO) under references ESP2014‐56138‐C3‐2‐R and ESP2107‐87690‐C3‐1‐R.

Producción Científica, This work aims to evaluate whether the multi-point analysis the ExoMars Raman Laser Spectrometer (RLS) will perform on powdered samples could serve to classify ultramafc rocks on Mars. To do so, the RLS ExoMars Simulator was used to study terrestrial analogues of Martian peridotites and pyroxenites by applying the operational constraints of the Raman spectrometer onboard the Rosalind Franklin rover. Besides qualitative analysis, RLS-dedicated calibration curves have been built to estimate the relative content of olivine and pyroxenes in the samples. These semi-quantitative results, combined with a rough estimate of the concentration ratio between clino- and ortho-pyroxene mineral phases, were used to classify the terrestrial analogues. XRD data were fnally employed as reference to validate Raman results. As this preliminary work suggests, ultramafc rocks on Mars could be efectively classifed through the chemometric analysis of RLS data sets. After optimization, the proposed chemometric tools could be applied to the study of the volcanic geological areas detected at the ExoMars landing site (Oxia Planum), whose mineralogical composition and geological evolution have not been fully understood, Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

This work is funded by the Spanish Ministerio de Economía y Competitividad (MINECO) under references ESP2014‐56138‐C3‐2‐R and ESP2107‐87690‐C3‐1‐R. We would like to thank The Austrian Space Forum (OeWF) and the AMADEE‐18 Oman National Steering Committee, in particular, Dr. Saleh Al‐Shidhani and the government and people of the Sultanate of Oman. The Planetary Exploration Instrumentation Laboratory (PIL) at York University is especially thankful for the financial support provided by the Natural Sciences and Engineering Research Council of Canada (NSERC), the Ontario Centre of Excellence (OCE), and the Canadian Space Agency. E. A. Lalla would like to express gratitude to the Ontario Centre of Excellence (OCE) for the TalentEdge Postdoctoral Funding during the development of the present manuscript. The authors are grateful to Dr. K. Tait and V. Di Cecco for the opportunity to carry out measurements at the Royal Ontario Museum (ROM) and their excellent support., Between February 1 and February 28, 2018, the Austrian Space Forum, in cooperation with research teams from 25 nations, conducted the AMADEE-18 mission—a human-robotic Mars expedition simulation in the Dhofar region in the Sultanate of Oman. As a part of the AMADEE-18 simulated Mars human exploration mission, the Remote Science Support team investigated the Dhofar area (Oman) to qualify it as a potential Mars analog site. The motivation of this research was to study and register selected samples collected by the analog astronauts during the AMADEE-18 mission with the European Space Agency (ESA) ExoMars Raman Laser Spectrometer (RLS) simulator, compare the results with standard laboratory measurements, and establish the implication of the results to the future ESA ExoMars mission. The Raman measurements identified minerals such as carbonates (calcite and dolomite), feldspar and plagioclase (albite, anorthite, orthoclase, and sanidine), Fe-oxides (goethite, hematite, and magnetite), and Ti-oxide (anatase), each relevant to planetary exploration. As we have presented here, Raman spectroscopy is a powerful tool for detecting the presence of organic molecules, particularly by analyzing the principal vibration of C-C and C-H bonds. It has also been shown that portable Raman spectroscopy is a relevant tool for in situ field studies such as those conducted during extra-vehicular activities (EVA) in simulated missions like the AMADEE-18 and the future AMADEE-2020 campaign., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737) ; Spanish Ministerio de Economía y Competitividad (MINECO) under references ESP2014‐56138‐C3‐2‐R and ESP2107‐87690‐C3‐1‐R

The Mastcam-Z Camera is a stereoscopic, multispectral camera with zoom ca pability on NASA’s Mars-2020 Perseverance rover. The Mastcam-Z relies on a set of two deck-mounted radiometric calibration targets to validate camera performance and to provide an instantaneous estimate of local irradiance and allow conversion of image data to units of reflectance (R∗ or I/F) on a tactical timescale. Here, we describe the heritage, design, and optical characterization of these targets and discuss their use during rover operations. The Mastcam-Z primary calibration target inherits features of camera calibration targets on the Mars Exploration Rovers, Phoenix and Mars Science Laboratory missions. This target will be regularly imaged during flight to accompany multispectral observations of the martian surface. The primary target consists of a gold-plated aluminum base, eight strong hollow cylinder Sm2Co17 alloy permanent magnets mounted in the base, eight ceramic color and grayscale patches mounted over the magnets, four concentric, ceramic grayscale rings and a central aluminum shadow post (gnomon) painted with an IR-black paint. The magnets are expected to keep the central area of each patch relatively free of Martian aeolian dust. The Mastcam-Z secondary calibration target is a simple angled aluminum shelf carrying seven vertically mounted ceramic color and grayscale chips and seven identical, but hori zontally mounted ceramic chips. The secondary target is intended to augment and validate the calibration-related information derived from the primary target. The Mastcam-Z radio metric calibration targets are critically important to achieving Mastcam-Z science objectives for spectroscopy and photometric properties, Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

In the present work, NIR, LIBS, Raman and XRD techniques have been complementarily used to carry out a comprehensive characterization of a terrestrial analogue selected from the Chesapeake Bay Impact Structure (CBIS). The obtained data clearly highlight the key role of Raman spectroscopy in the detection of minor and trace compounds, through which inferences about geological processes occurred in the CBIS can be extrapolated. Beside the use of commercial systems, further Raman analyses were performed by the Raman Laser Spectrometer (RLS) ExoMars Simulator. This instrument representsthe most reliable tool to effectively predict the scientific capabilities of the ExoMars/Raman system that will be deployed on Mars in 2021. By emulating the analytical procedures and operational restrictions established by the ExoMars mission rover design, it was proved that the RLS ExoMars Simulator is able to detect the amorphization of quartz, which constitutes an analytical clue of the impact origin of craters. On the other hand, the detection of barite and siderite, compounds crystallizing under hydrothermal conditions, helps to indirectly confirm the presence of water in impact targets. Furthermore, the RLS ExoMars Simulator capability of performing smart molecular mappings was also evaluated. According to the obtained results, the algorithms developed for its operation provide a great analytical advantage over most of the automatic analysis systems employed by commercial Raman instruments, encouraging its application for many additional scientific and commercial purposes., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

Raman and laser-induced breakdown spectroscopy (LIBS) spectroscopies will play an important role in planetary exploration missions in the following years, not only with Raman instruments like Raman laser spectrometer on board of Rosalid Franklin Rover or scanning habitable environments with Raman and luminescence for organics and chemicals on board Mars2020 Rover but also with combined instruments such as SuperCam. These techniques will be part of the upcoming planetary exploration missions because they can provide complementary information from the analysed sample while potentially sharing hardware components, maximizing the scientific return of the samples while limiting mass. In this framework, this study seeks to test the feasibility of combining several univariate and multivariate analysis techniques with data fusion techniques of different instruments (532 and 785 nm Raman and LIBS) to evaluate the improvements in the quantitative classification of samples in binary mixtures. We prepared two-component mixtures that are potentially relevant in planetary exploration missions, using two different sulfates and a chloride. A more accurate classification of the samples is possible through a univariate analysis that combines the calculated concentration indicators for Raman and LIBS. On the other hand, multivariate analysis was run on Raman, LIBS, and Raman + LIBS low-level fused data sets. The results showed a better improvement when fusing LIBS and Raman when compared with the redundant fusion but not a systematic improvement when compared with individual sets. We demonstrate that a quantification of the mineral abundances in binary mixtures can be obtained from Raman and LIBS data using univariate and multivariate analysis techniques, being the latter remarkably better, moving from performances of classification, in the whole range of concentrations, that could be over the 10% to values under 3.5%. Furthermore, the fusion of data coming from these techniques improves the classification limit with respect to the individual techniques. Thus, besides the (evident) hardware convenience of combining LIBS with 532-nm Raman, there could be analytical advantages as well., With funding from the Spanish government through the "María de Maeztu Unit of Excellence" accreditation (MDM-2017-0737)

International audience; 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 (SiO2, TiO2, Al2O3, FeOT, MgO, CaO, Na2O, K2O), 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.

Producción Científica, This work presents the latest chemometric tools developed by the RLS science team to optimize the scientific outcome of the Raman system onboard the ExoMars 2022 rover. Feldspar, pyroxene and olivine samples were first analyzed through the RLS ExoMars Simulator to determine the spectroscopic indicators to be used for a proper discrimination of mineral phases on Mars. Being the main components of Martian basaltic rocks, lepidocrocite, augite and forsterite were then used as mineral proxies to prepare binary mixtures. By emulating the operational constraints of the RLS, Raman datasets gathered from laboratory mixtures were used to build external calibration curves. Providing excellent coefficients of determination (R2 0.9942÷0.9997), binary curves were finally used to semi-quantify ternary mixtures of feldspar, pyroxene and olivine minerals. As Raman results are in good agreement with real concentration values, this work suggests the RLS could be effectively used to perform semi-quantitative mineralogical studies of the basaltic geological units found at Oxia Planum. As such, crucial information about the geological evolution of Martian Crust could be extrapolated. In light of the outstanding scientific impact this analytical method could have for the ExoMars mission, further methodological improvements to be discussed in a dedicated work are finally proposed., Consejo Europeo de Investigación (grant 687302), Ministerio de Economía, Industria y Competitividad (grants PID2019-107442RB-C31 and RDE2018-102600-T)

Producción Científica, We present the compositional analysis of three terrestrial analogues of Martian olivine-bearing rocks derived from both laboratory and flight-derived analytical instruments. In the first step, state-of-the-art spectroscopic (XRF, NIR and Raman) and diffractometric (XRD) laboratory systems were complementary used. Besides providing a detailed mineralogical and geochemical characterization of the samples, results comparison shed light on the advantages ensured by the combined use of Raman and NIR techniques, being these the spectroscopic instruments that will soon deploy (2021) on Mars as part of the ExoMars/ESA rover payload. In order to extrapolate valuable indicators of the mineralogical data that could derive from the ExoMars/Raman Laser Spectrometer (RLS), laboratory results were then compared with the molecular data gathered through the RLS ExoMars Simulator. Beside correctly identifying all major phases (feldspar, pyroxene and olivine), the RLS ExoMars Simulator confirmed the presence of additional minor compounds (i.e. hematite and apatite) that were not detected by complementary techniques. Furthermore, concerning the in-depth study of olivine grains, the RLS ExoMars simulator was able to effectively detect the shifting of the characteristic double peak around 820 and 850 cm 1 , from which the Fe-Mg content of the analysed crystals can be extrapolated. Considering that olivine is one of the main mineral phases of the ExoMars landing site (Oxia Planum), this study suggests that the ExoMars/RLS system has the potential to provide detailed information about the elemental composition of olivine on Mars., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

Producción Científica, The multi analytical study of terrestrial analogues is a useful strategy to deepen the knowledge about the geological and environmental evolution of Mars and other extraterrestrial bodies. In spite of the increasing importance that LIBS, NIR and Raman techniques are acquiring in the field of space exploration, there is a lack web-based platform providing free access to a wide multi-spectral database of terrestrial analogue materials. The Planetary Terrestrial Analogue Library (PTAL) project aims at responding to this critical need by developing and providing free web accessibility to LIBS, NIR and Raman data from more than 94 terrestrial analogues selected according to their congruence with Martian geological contexts. In this framework, the present manuscript provides the scientific community with a complete overview of the over 4500 Raman spectra collected to feed the PTAL database. Raman data, obtained through the complementary use of laboratory and spacecraft-simulator systems, confirmed the effectiveness of this spectroscopic technique for the detection of major and minor mineralogical phases of the samples, the latter being of critical importance for the recognition of geological processes that could have occurred on Mars and other planets. In light of the forthcoming missions to Mars, the results obtained through the RLS ExoMars Simulator offer a valuable insight on the scientific outcome that could derive from the RLS spectrometer that will soon land on Mars as part of the ExoMars rover payload. (13) (PDF) PTAL multi-spectral database of planetary terrestrial analogues: Raman data overview. Available from: https://www.researchgate.net/publication/348675482_PTAL_multi-spectral_database_of_planetary_terrestrial_analogues_Raman_data_overview [accessed Apr 19 2021]., Proyecto MINECO Retos de la Sociedad. Ref. ESP2017-87690-C3-1-R

[ES]El reciente descubrimiento de minerales hidratados sobre la superficie de Marte sugiere la presencia de importantes cantidades de agua líquida durante algunas etapas de su historia geológica. A raíz de este hallazgo, los estudios sobre minerales hidratados en ambientes terrestres como potenciales análogos marcianos han adquirido gran relevancia. En el presente trabajo se han estudiado las características mineralógicas y geoquímicas de minerales hidratados procedentes de varias cuevas y minas españolas y de la región minera de Iglesias-Carbonia (Cerdeña, Italia) mediante técnicas espectroscópicas implicadas en misiones de exploración marciana presentes y futuras, con el fin de evaluar su potencial para la detección de este tipo de minerales. Por un lado, se ha utilizado la espectroscopia Raman, que formará parte de la carga científica de la misión ExoMars de la Agencia Espacial Europea. Por otro lado, la espectroscopia de IR, otra de las técnicas involucradas en esta misión de la ESA, así como la espectroscopia LIBS y la combinación de difracción-fluorescencia de rayos X (DRX-FRX), ambas a bordo de la misión MSL de la NASA. Estas técnicas han permitido identificar sulfatos (yeso, epsomita, jarosita y glaucocerinita), silicatos (hemimorfita) y carbonatos (hidrocincita e hidromagnesita), todos ellos minerales hidratados y algunos de los cuales también han sido descritos en Marte. Por otro lado, se han abordado los procesos de formación de estos minerales y las potenciales analogías con la mineralogénesis en Marte. Del conjunto de técnicas empleadas, la combinación Raman-LIBS se perfila como la opción más eficiente para la detección de minerales hidratados en condiciones marcianas., [EN] The recent discovery of hydrated sulfates on the Martian surface suggests that widespread wet conditions were present during its early geological history. Upon this discovery, a growing interest has emerged in the study of this group of minerals from terrestrial environments as potential Martian analogs. Here, we evaluate the potential of various analytical techniques involved in current and future mission to Mars for detecting hydrated minerals from caves and mines of Spain and the mining district of Iglesias-Carbonia (Sardinia, Italy). Minerals were analyzed by Raman spectroscopy, which will be included in the payload of the ESA’s 2018 ExoMars mission. On the other hand, IR spectroscopy, also included in the ExoMars mission, as well as LIBS spectroscopy and a combined XRD-XRF analyzer, both onboard the Curiosity rover of NASA’s MSL mission, were utilized. Hydrated sulfates (gypsum, epsomite, jarosite and glaucocerinite), silicates (hemimorphite) and carbonates (hydrozincite and hydromagnesite) were characterized. Most of these minerals have also been detected on the Martian surface. The mechanisms involved in the genesis of these minerals and the potential analogies with the minerogenesis on Mars are discussed. The Raman-LIBS combination appears to be the most powerful tool for detecting hydrated minerals in Martian conditions. This technology will probably be considered to be onboard of further planetary missions

ExoFit trials are field campaigns financed by ESA to test the Rosalind Franklin rover and to enhance collaboration practices between ExoMars working groups. During the first trial, a replicate of the ExoMars rover was remotely operated from Oxfordshire (United Kingdom) to perform a complex sequence of scientific operation at the Tabernas Desert (Spain). By following the ExoMars Reference Surface Mission (RSM), the rover investigated the Badlands subsoil and collected drill cores, whose analytical study was entrusted to the RLS (Raman Laser Spectrometer) team. The preliminary characterization of core samples was performed in-situ through the RLS Engineering and Qualification Model (EQM-2) and the Raman Demonstrator (RAD1), being this a new, portable emulator of the RLS. In-situ results where then complemented by laboratory analysis using the RLS ExoMars simulator and the commercial version of the Curiosity/CheMin XRD system. Raman data, obtained by closely simulating the operational constraints of the mission, successfully disclosed the mineralogical composition of the samples, reaching the detection of minor/trace phases that were not detected by XRD. More importantly, Raman analysis detected many organic functional groups, proving the presence of extremophile organisms in the arid sub-surface of the Tabernas Desert. In light of the forthcoming ExoMars mission, the results here presented proves that RLS could play a critical role in the characterization of Martian sub-surface environments and in the analytical detection of potential traces of live tracers., Comment: 16 pages, 7 figures, 1 table