Spectroscopic study of terrestrial analogues to support rover missions to Mars - A Raman-centred review.

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.

Raman Characterization of the CanMars Rover Field Campaign Samples Using the Raman Laser Spectrometer ExoMars Simulator: Implications for Mars and Planetary Exploration.

The Mars 2020 Perseverance rover landed on February 18, 2021, and has started ground operations. The ExoMars Rosalind Franklin rover will touch down on June 10, 2023. Perseverance will be the first-ever Mars sample caching mission-a first step in sample return to Earth. SuperCam and Scanning Habitable Environments with Raman & Luminescence for Organics & Chemicals (SHERLOC) on Perseverance, and Raman Laser Spectrometer (RLS) on Rosalind Franklin, will comprise the first ever in situ planetary mission Raman spectroscopy instruments to identify rocks, minerals, and potential organic biosignatures on Mars' surface. There are many challenges associated when using Raman instruments and the optimization and quantitative analysis of resulting data. To understand how best to overcome them, we performed a comprehensive Raman analysis campaign on CanMars, a Mars sample caching rover analog mission undertaken in Hanksville, Utah, USA, in 2016. The Hanksville region presents many similarities to Oxia Planum's past habitable conditions, including liquid water, flocculent, and elemental compounds (such as clays), catalysts, substrates, and energy/food sources for life. We sampled and conducted a complete band analysis of Raman spectra as mission validation analysis with the RLS ExoMars Simulator or RLS Sim, a breadboard setup representative of the ExoMars RLS instrument. RLS Sim emulates the operational behavior of RLS on the Rosalind Franklin rover. Given the high fidelity of the Mars analog site and the RLS Sim, the results presented here may provide important information useful for guiding in situ analysis and sample triage for caching relevant for the Perseverance and Rosalind Franklin missions. By using the RLS Sim on CanMars samples, our measurements detected oxides, sulfates, nitrates, carbonates, feldspars, and carotenoids, many with a higher degree of sensitivity than past results. Future work with the RLS Sim will aim to continue developing and improving the capability of the RLS system in the future ExoMars mission.

UV Time-Resolved Laser-Induced Fluorescence Spectroscopy of Amino Acids Found in Meteorites: Implications for Space Science and Exploration.

Laser-induced fluorescence spectroscopy is a useful laboratory and in situ technique for planetary exploration, with applications in biosignature detection and the search for life on Mars. However, little work has been completed on the utility of fluorescence spectroscopy techniques on asteroid relevant material. In preparation for asteroid sample return missions such as NASA's OSIRIS-REx and JAXA's Hayabusa2, we conducted UV time resolved laser-induced fluorescence spectroscopy (TR-LIF) analysis of 10 amino acids, all of which have been found in the carbonaceous meteorites Murchison and Allende. We present the calculation of decay rates of each amino acid (1.55-3.56 ns) and compare with those of relevant homogeneous minerals (15-70 ns). Moreover, we demonstrate a linear relationship between calculated lifetimes and elemental abundance of nitrogen and carbon (p < 0.025). The quantitative and qualitative fluorescence analyses presented in this work will lead to more reliable identification of organic material within meteorites and asteroids in a time-efficient, minimally destructive way.

Combined Spectroscopic Analysis of Terrestrial Analogs from a Simulated Astronaut Mission Using the Laser-Induced Breakdown Spectroscopy (LIBS) Raman Sensor: Implications for Mars.

One of the primary objectives of planetary exploration is the search for signs of life (past, present, or future). Formulating an understanding of the geochemical processes on planetary bodies may allow us to define the precursors for biological processes, thus providing insight into the evolution of past life on Earth and other planets, and perhaps a projection into future biological processes. Several techniques have emerged for detecting biomarker signals on an atomic or molecular level, including laser-induced breakdown spectroscopy (LIBS), Raman spectroscopy, laser-induced fluorescence (LIF) spectroscopy, and attenuated total reflectance Fourier transform infrared (ATR FT-IR) spectroscopy, each of which addresses complementary aspects of the elemental composition, mineralogy, and organic characterization of a sample. However, given the technical challenges inherent to planetary exploration, having a sound understanding of the data provided from these technologies, and how the inferred insights may be used synergistically is critical for mission success. In this work, we present an in-depth characterization of a set of samples collected during a 28-day Mars analog mission conducted by the Austrian Space Forum in the Dhofar region of Oman. The samples were obtained under high-fidelity spaceflight conditions and by considering the geological context of the test site. The specimens were analyzed using the LIBS-Raman sensor, a prototype instrument for future exploration of Mars. We present the elemental quantification of the samples obtained from LIBS using a previously developed linear mixture model and validated using scanning electron microscopy energy dispersive spectroscopy. Moreover, we provide a full mineral characterization obtained using ultraviolet Raman spectroscopy and LIF, which was verified through ATR FT-IR. Lastly, we present possible discrimination of organics in the samples using LIF and time-resolved LIF. Each of these methods yields accurate results, with low errors in their predictive capabilities of LIBS (median relative error ranging from 4.5% to 16.2%), and degree of richness in subsequent inferences to geochemical and potential biochemical processes of the samples. The existence of such methods of inference and our ability to understand the limitations thereof is crucial for future planetary missions, not only to Mars and Moon but also for future exoplanetary exploration.

ExoMars Raman Laser Spectrometer: A Tool to Semiquantify the Serpentinization Degree of Olivine-Rich Rocks on Mars.

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.

Laboratory Analysis of Returned Samples from the AMADEE-18 Mars Analog Mission.

Between February 1 and 28, 2018, the Austrian Space Forum, in cooperation with the Oman Astronomical Society and 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 performed analyses of the Dhofar area (Oman) in an effort to characterize the region as a potential Mars analog site. The main motivation of this research was to study and register selected samples collected by analog astronauts during the AMADEE-18 mission with laboratory analytical methods and techniques comparable with those that are likely to be used on Mars in the future. The 25 samples representing unconsolidated sediments obtained during the simulated mission were studied by using optical microscopy, Raman spectroscopy, X-ray diffraction, laser-induced breakdown spectroscopy, and laser-induced fluorescence spectroscopy. The principal results show the existence of minerals and alteration processes related to volcanism, hydrothermalism, and weathering. The analogy between the Dhofar region and the Eridana Basin region of Mars is clearly noticeable, particularly as an analog for secondary minerals formed in a hydrothermal seafloor volcanic-sedimentary environment. The synergy between the techniques used in the present work provides a solid basis for the geochemical analyses and organic detection in the context of future human-robotic Mars expeditions. AMADEE-18 has been a prime test bed for geoscientific workflows with astrobiological relevance and has provided valuable insights for future space missions.

The AMADEE-18 Mars Analog Expedition in the Dhofar Region of Oman.

From February 1 to 28, 2018, the Austrian Space Forum, in cooperation with the Oman Astronomical Society and 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. A carefully selected field crew, supported by a Mission Support Center in Innsbruck, Austria, conducted 19 experiments relevant to astrobiology, engineering disciplines, geoscience, operations research, and human factors. This expedition was the 12th in a series of analog missions that emulate selected aspects of the science expected for a human Mars mission, including the characterization of the (paleo)geological environment, human factors studies, and the search for biomarkers. In particular, an Exploration Cascade was deployed as a suggested workflow for coordinating the timing and location of the respective instruments and experiments. In validation of this workflow, the decision-making interaction between the field and the Mission Support Center was studied. This article introduces the AMADEE-18 mission and provides the mission-specific context for the other contributions of this special issue.

ExoMars Raman Laser Spectrometer (RLS): development of chemometric tools to classify ultramafic igneous rocks on Mars.

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 ultramafic 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 finally employed as reference to validate Raman results. As this preliminary work suggests, ultramafic rocks on Mars could be effectively classified 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.

Clinical anisotropy: A case for shared decision making in the age of too much data and patient dis-integration.

Today, in the age of big data, we are more capable than ever before. But even having the world at our disposal with naught but the touch of a button, we find ourselves exceedingly vulnerable in the patient chair. With insurmountable amounts of knowledge being published and disseminated around the world, how can clinicians keep up and what can be done about it? And sitting in the patient chair, bewildered by the ever-changing landscape of medicine at the blink of an eye, how can we, as patients, ever hope to be part of the conversations revolving around our own health? In this work, we explore the present-day problems of big data in the clinical context, how failing to integrate patients can result in detrimental outcomes, and what shared decision making can do about it.