Jose Antonio Manrique

Mars is primarily composed of mafic mineral assemblages and their alteration products, but small, scattered rocks strewn across the landscape offer clues to greater petrological diversity. While traversing the Jezero crater rim, the Perseverance rover encountered several plagioclase‐rich light‐toned float rocks. SuperCam identified the distinctive signature of corundum (α‐Al ₂ O ₃ ) in these rocks using time‐resolved luminescence spectroscopy. Two strong peaks (692.7 and 694.1 nm) with millisecond lifetimes, and additional supporting lines, are consistent with Cr ³⁺ substitution for Al ³⁺ in corundum. Corundum forms in Al‐rich, Si‐depleted environments through magmatic or metamorphic processes. Given the rocks' small size, association with plagioclase, and location on the crater rim, we interpret the most plausible formation scenario to be impact induced metamorphism at the interface of a felsic and a mafic/ultramafic member with the likely action of fluids at some stage, although other possibilities are not excluded.

The detection of organic molecules at trace concentration levels remains a critical challenge for astrobiology research. While Raman spectroscopy is a powerful and well-established technique for planetary surface investigations, its intrinsic sensitivity often limits the detection of low-abundance biomarkers. Surface-Enhanced Raman Spectroscopy (SERS) offers orders-of-magnitude signal enhancement but has so far faced significant limitations for space applications, particularly in terms of reproducibility, stability, and long-term operability.,In this work, we present the development and validation of a microfluidic chip specifically designed for the on-chip synthesis of plasmonic silver nanoemulsions and their direct application to SERS analysis. The system enables the controlled and reproducible generation of fresh SERS-active nanoemulsions immediately prior to analysis. The system was tasted by using the ExoMars Raman Laser Spectrometer Simulator (RLS-SIM) to analyze nucleobases (as biomarker proxies) directly on chip. Detection limits between 10⁻⁷ and 10⁻¹¹ M were achieved, representing an improvement of up to seven orders of magnitude compared to conventional Raman measurements.,These results demonstrate the strong potential of combining microfluidics and SERS for highly sensitive, reproducible, and compact analytical platforms compatible with planetary exploration constraints. The proposed approach represents a significant step toward the implementation of Raman/SERS hybrid systems for future astrobiology missions aimed at the detection of trace organic compounds on planetary surfaces.

Over 3.5 years of exploration in Jezero Crater, the Perseverance rover has explored several geological units of diverse origins and natures, performing multi‐technique remote analyses of the chemistry and mineralogy of rocks with the SuperCam instrument suite. Three of these units are dominated by mafic to ultramafic rocks: the igneous rocks of Séítah (olivine cumulate on the crater floor), the sedimentary rocks of the Upper Fan (Western delta) and the Margin Unit, of likely igneous origin. Despite their diverse natures, these three different units present similar mineralogical assemblages with: (a) primary igneous minerals (olivine, pyroxene, Cr‐rich Ti‐Fe oxides), (b) Fe‐Mg carbonate, (c) hydrated/hydroxylated silica, and (d) phyllosilicates. The abundance of carbonate is variable, and we estimate it around 3–9 wt.% and up to 6–16 wt.% carbonate mineral in the Upper Fan and Margin Unit, respectively. We propose that most of these carbonates formed through in situ carbonation of mafic/ultramafic material, whether these rocks were emplaced through igneous or sedimentary processes. The distribution of carbonate with elevation in the Upper Fan and Margin Unit suggests a contribution of the lacustrine activity to the carbonate process, possibly enhanced by hydrothermal activity. These in situ observations may be extrapolated to other carbonates‐bearing rocks on Mars and would make the amount of carbon potentially stored in Martian ultramafic rocks overall significant. This would suggest that carbonation of ultramafic rocks might have played a key role in pumping CO ₂ from and therefore in cooling the Martian atmosphere.

The Mars 2020 Perseverance rover introduced Raman spectroscopy to in situ planetary exploration for the first time when it landed in Jezero crater on Mars in February 2021. The SuperCam instrument onboard Perseverance is a multi‐analytical tool capable of acquiring time‐resolved Raman data from Martian targets at standoff distances of a few meters. This is a particularly challenging task due to the operational constraints, the harsh conditions on the Martian surface, and especially the very fine‐grained nature of the Martian soil. To address these challenges, the SuperCam Raman team has invested significant effort into optimizing both the acquisition and post‐processing of Raman data collected on Mars, as detailed in this work. Additionally, this paper reviews and discusses the detections made by SuperCam Raman during the first 1,000 sols (almost 3 Earth years) of the Mars 2020 mission. During this period, SuperCam Raman data provided key insights into the mineralogy of Jezero throughout the Crater, Delta, and Margin Campaigns. Key detections include olivine, carbonates, perchlorates, and sulfates (such as anhydrite), identified in both abraded patches and natural surfaces. The high specificity of Raman spectroscopy enables the unequivocal identification of these minerals, allowing for rapid and direct interpretation of Jezero's mineralogy, especially when combined with other techniques from SuperCam or others on the rover. Furthermore, this paper compiles the spectra acquired from the SuperCam Calibration Target samples on Mars, including studies on the degradation of the Ertalyte (PET), an organic polymer sample and analyses of diamond, apatite, and other reference materials.

Garnets are minerals offering valuable insights into geological and planetary processes, in both terrestrial and extraterrestrial contexts. Their presence in metamorphic rocks, as well as in meteorites, makes them key indicators of the conditions under which they formed, such as pressure, temperature, and chemical environment. This information is valuable for understanding the history and evolution of planetary bodies, including Earth and Mars. Developing automatic classification models for garnets using Raman spectroscopy has a potential application for planetary exploration, particularly for the Raman Laser Spectrometer (RLS) on the Rosalind Franklin rover of the upcoming ExoMars mission. In this work, we used a dataset combining spectra from ADAMM and RRUFF databases, ensuring a well‐distributed representation of the two main garnet groups: pyralspites and ugrandites. The spectra from ADAMM were obtained using the RLS SIM, a laboratory version of RLS, while RRUFF data helped increase the number of samples in the dataset. After standardizing all data, we designed a two‐step classification model: a top‐level model to classify into the two main groups and two specific models to classify the garnet type within each group. We tested multiple machine learning algorithms, including support vector machine (SVM), k‐nearest neighbors (KNN), artificial neural networks (ANN), decision tree, and naive Bayes. The top‐level classification reached 100% accuracy in testing, while the final combined model achieved 80.42% accuracy. These results demonstrate that machine learning and Raman spectroscopy can effectively classify garnets, providing a valuable tool for planetary missions and mineralogical studies.

The Perseverance rover has explored and sampled igneous and sedimentary rocks within Jezero Crater to characterize early Martian geological processes and habitability and search for potential biosignatures^1-7. Upon entering Neretva Vallis, on Jezero Crater's western edge⁸, Perseverance investigated distinctive mudstone and conglomerate outcrops of the Bright Angel formation. Here we report a detailed geological, petrographic and geochemical survey of these rocks and show that organic-carbon-bearing mudstones in the Bright Angel formation contain submillimetre-scale nodules and millimetre-scale reaction fronts enriched in ferrous iron phosphate and sulfide minerals, likely vivianite and greigite, respectively. This organic carbon appears to have participated in post-depositional redox reactions that produced the observed iron-phosphate and iron-sulfide minerals. Geological context and petrography indicate that these reactions occurred at low temperatures. Within this context, we review the various pathways by which redox reactions that involve organic matter can produce the observed suite of iron-, sulfur- and phosphorus-bearing minerals in laboratory and natural environments on Earth. Ultimately, we conclude that analysis of the core sample collected from this unit using high-sensitivity instrumentation on Earth will enable the measurements required to determine the origin of the minerals, organics and textures it contains.

The Atmospheric Chamber for Measurements in Environment (A.C.M.E.) provides a versatile and highly controlled environment for simulating planetary conditions, supporting the testing and calibration of instruments for planetary exploration. In this study, we utilized A.C.M.E. to evaluate the performance of a novel hollow‐core fiber (HCF) Raman gas sensor prototype developed by the ERICA research team. By integrating the HCF sensor with a dedicated spectrometer, we confirmed that Raman spectrometers, such as the Raman Laser Spectrometer (RLS), could be used for atmospheric gas analysis in future planetary missions, expanding their applications beyond mineralogical studies. By using the A.C.M.E. chamber to produce representative gas mixtures, this work analytically demonstrated that, once optimized, the HCF sensor prototype could be potentially used to investigate the atmosphere of both Mars and Venus in future planetary missions. These findings underscore the critical role of atmospheric chambers like A.C.M.E. in advancing technologies for future planetary exploration missions.

The formation of craters on the surface of Mars is primarily attributable to the impact of celestial bodies. This impact results in the generation of elevated temperatures and pressures, resulting in the formation of high-temperature and high-pressure minerals [1]. This is the case of the Jezero crater, landing site of the Mars 2020 mission's Perseverance rover. This rover is currently analyzing the crater rim of the mentioned crater, an area where high-pressure minerals may be present.One of the techniques on board the rover is Raman spectroscopy, which is part of the SuperCam and SHERLOC instruments. This technique can determine the presence of high-pressure minerals by analyzing the shift of the Raman bands. In some cases, calibrating the Raman band position, the pressure to which certain compounds were subjected can be estimated. However, it should be noted that not all minerals behave in the same way in Raman spectroscopy when subjected to high-pressures. On the one hand, some minerals are transformed into other mineral phases because of high-pressure, usually their corresponding high-pressure polymorphs. On the other hand, other minerals exhibit a shift in the position of their Raman bands towards higher wavenumbers when exposed to high-pressures.This study presents a compilation of minerals under high-pressure conditions that may likely be found on the Jezero crater rim and their behavior as observed through Raman spectroscopy.Table 1 summarizes a selection of the minerals most likely to be encountered on Mars which, upon exposure to high-pressures, are known to undergo phase transformations. The table lists the high-pressure mineral name, the Raman band position of this mineral, the pressure and/or temperature at which it is formed and the original mineral from which the new mineral phase is formed.Conversely, Table 2 displays the minerals that exhibit Raman shift towards higher wavenumbers when subjected to high-pressure conditions. The mineral names, the position of the Raman band at ambient conditions, the position of the Raman band at the maximum pressure studied in the literature and the value of this pressure, are included in the table.Table 1. High-pressure minerals [2,3].Table 2. Minerals whose Raman bands shift to higher wavenumbers with pressure [4,5,6].It is important to note that certain compounds may also undergo Raman band movements due to cation exchange. This is the case of feldspar, siderite, calcite, magnesite and dolomite in Table 2. However, it may be considered that Raman band shifts can occur due to cation exchanges or enrichments. Therefore, detected Raman shifts must be always studied in parallel to elemental characterization and stoichiometric calculations to attribute an accurate origin to the observed wavelength movement. In the case of Perseverance rover, LIBS (laser-induced breakdown spectroscopy) MOC (major-element composition) values can be crucial for the Raman spectroscopy accurate result interpretation at the Crater Rim. It is worthy to highlight that some of these minerals have been identified in Martian meteorites, such as maskelynite in the NorthWest Africa (NWA) 1195 meteorite [7], coesite in the NWA 8657 [8] or high-pressure calcite [9]. Given the prevalence of these minerals in samples with a Martian origin, there is a high probability of their occurrence in crater rims on the planet's surface.References[1] Pang, RL., Zhang, AC. et al. High-pressure minerals in eucrite suggest a small source crater on Vesta. Sci Rep 6, 26063 (2016). https://doi.org/10.1038/srep26063[2] Manuputty, M.Y., Dreyer, J.A. et al. Polymorphism of nanocrystalline TiO2 prepared in a stagnation flame: formation of the TiO2-II phase. Chem. Sci. 5 (2019). http://xlink.rsc.org/?DOI=c8sc02969e.[3] Ohtani, E., Kimura, Y. et al. Formation of high-pressure minerals in shocked L6 chondrite Yamato 791384: constraints on shock conditions and parent body size. Earth Planet. Sci. Lett. 227, 3-4, 505-515 (2004). https://doi.org/10.1016/j.epsl.2004.08.018.[4] Coloma, L., Aramendia, J. et al. Raman calibration of shocked Ca-, Mg- and Fe-carbonates. Tenth International Conference on Mars 2024, 3007.[5] Sims, M., Johnson, J.R. et al. Unconventional high-pressure Raman spectroscopy study of kinetic and peak pressure effects in plagioclase feldspars. Phys. Chem. Miner. 47 (2020). https://doi.org/10.1007/s00269-020-01080-z.[6] Johnson, J.R., Jaret, S.J. et al. Raman and infrared microspectroscopy of experimentally shocked basalts. J. Geophys. Res. Planets. 125, 2 (2020). https://doi.org/10.1029/2019JE006240.[7] Ray, D., Misra, S. et al. Maskelynite- as seen in shocked Lonar target basalt, India, and martian and lunar meteorites. Geochem. 84, 2 (2024). https://doi.org/10.1016/j.chemer.2024.126127.[8] Hu, S., Li, Y. et al. Discovery of coesite from the martian shergottite Northwest Africa 8657. Geochim. Cosmochim. Acta. 286, 404-417 (2020). https://doi.org/10.1016/j.gca.2020.07.021.[9] Coloma, L., García-Florentino, C. et al. Development of non-destructive analytical strategies based on Raman spectroscopy and complementary techniques for Mars Sample Return tested on Northwest Africa 1950 Martian meteorite. J. Raman Spectrosc. 53, 12, 2068-2085 (2022). https://doi.org/10.1002/jrs.6445. AcknowledgementsThis work is supported by the PAMMAT project “Alteration processes in Mars and Moon Meteorites, and Terrestrial Analogues at different environments: Mars2020, Rosalind Franklin and Returned Samples from Mars and Moon” (Grant No. PID2022-142750OB-I00), funded by the Spanish Agency for Research (through the Spanish Ministry of Science and Innovation, MCIN, and the European Regional Development Fund, FEDER, MCIN/AEI/10.13039/501100011033/FEDER,UE), and the Strategic Project “Study of Alteration Processes in Terrestrial and Planetary Materials” (Grant No. UPV/EHU PES21/88), funded by the UPV/EHU.

Over the last decade, Raman spectroscopy has established itself as a fundamental technique for planetary exploration and the geological characterization of bodies in our Solar System. ESA has been evaluating combinations of analytical methods combined in a portable, handheld analytical tool for planetary surface exploration missions, with the potential use‐case being human missions to the surface of the Moon (e.g., in the frame of the NASA‐led Artemis program). Based on the Raman technique, we report on a development that seeks to complement Raman with other techniques for determining chemical composition, such as LIBS or XRF, and also provided with a close‐up imager integrated into the instruments to obtain context images of the analyzed samples, to determine their texture and help select the point of analysis. For this design, portability and ergonomic considerations are also being taken into account, since they must be operated by future astronauts quickly and efficiently. Breadboard instruments developed in the frame of an ESA contract are designed to interface wirelessly with an electronic field book and are usable not just in a laboratory environment but also as training equipment on Earth during the analogue field campaigns of its astronauts within the PANGAEA program. This work shows the performance obtained by one of the two Portable Handheld cOmbinEd RamaN‐LIBS‐XRF (PHOENIX) instruments developed within the framework of this ESA contract.

The Mars2020 Perseverance rover introduced Raman spectroscopy to in-situ planetary exploration for the first time when it landed in Jezero crater on Mars in February 2021. The SuperCam instrument onboard Perseverance is a multi-analytical tool capable of acquiring time-resolved Raman data from Martian targets at standoff distances of a few meters. This is a particularly challenging task due to the operational constraints, the harsh conditions on the Martian surface, and especially the very fine-grained nature of the Martian samples. To address these challenges, the SuperCam Raman team has invested significant effort into optimizing both the acquisition and post-processing of Raman data collected on Mars, as detailed in this work. Additionally, this paper reviews and discusses the detections made by SuperCam Raman during the first 1000 sols (almost 3 Earth years) of the Mars2020 mission. During this period, SuperCam Raman data provided key insights into the mineralogy of Jezero throughout the Crater, Delta, and Margin Campaigns. Key detections include olivine, carbonates, perchlorates, and sulfates (such as anhydrite), identified in both abraded patches and natural surfaces. The high specificity of Raman spectroscopy enables the unequivocal identification of these minerals, allowing for rapid and direct interpretation of Jezero’s mineralogy, especially when combined with other techniques from SuperCam or others on the rover. Furthermore, this paper compiles, reviews, and discusses the spectra acquired from the SuperCam Calibration Target (SCCT) samples on Mars, including studies on the degradation of the ertalyte organic sample and analyses of diamond, apatite, and other reference materials.