Raman Laser Spectrometer Instrument Research Articles

Semi‐quantification of binary saline solutions by Raman spectroscopy: Implications for Europa

AbstractThe 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.

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.

The Raman Laser Spectrometer: A performance study using ExoMars representative crushed samples

AbstractThe Raman Laser Spectrometer (RLS) is one of three key analytical instruments incorporated within the body of the ExoMars 2022 rover. The rover will collect samples from different sites on the Oxia Planum plain, using a drill capable of penetrating the near subsurface and rocky outcrops to a depth of 2 m. Samples are passed to the Analytical Laboratory Drawer (ALD) in the heart of the rover vehicle, where the Sample Preparation and Distribution System (SPDS) processes and transports the crushed material into a refillable container (RC), which is then presented to the analytical instruments for exobiology and geological investigation. The final sample grain distribution of the powder sample following the crushing and flattening processes is a critical aspect of the RLS instrument that has a direct impact on its overall performance, related to its mineral identification and operational capabilities. This paper provides a comparative overview of the performance of a set of Raman instruments, the RLS micro‐Raman Laboratory Equipment, the RLS ExoMars Simulator, and the RLS Engineering and Qualification Model (EQM) using Martian representative crushed samples, along with an evaluation of instrument performance as a function of the operational scenario. The results from the work performed by the RLS team confirm the capability of the RLS instrument performances, by acquiring good‐quality spectra from crushed samples provided by the SPDS, whose science return can be further optimized when improving the RLS instrument operation sequence.

The Raman laser spectrometer ExoMars simulator (RLS Sim): A heavy‐duty Raman tool for ground testing on ExoMars

AbstractThe 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.

Raman analysis of a shocked planetary surface analogue: Implications for habitability on Mars

AbstractThe scientific aims of the ExoMars Raman laser spectrometer (RLS) include identifying biological signatures and evidence of mineralogical processes associated with life. The RLS instrument was optimised to identify carbonaceous material, including reduced carbon. Previous studies suggest that reduced carbon on the Martian surface (perhaps originating from past meteoric bombardment) could provide a feedstock for microbial life. Therefore, its origin, form, and thermal history could greatly inform our understanding of Mars' past habitability. Here, we report on the Raman analysis of a Nakhla meteorite analogue (containing carbonaceous material) that was subjected to shock through projectile impact to simulate the effect of meteorite impact. The characterisation was performed using the RLS Simulator, in an equivalent manner to that planned for ExoMars operations. The spectra obtained verify that the flight‐representative system can detect reduced carbon in the basaltic sample, discerning between materials that have experienced different levels of thermal processing due to impact shock levels. Furthermore, carbon signatures acquired from the cratered material show an increase in molecular disorder (and we note that this effect will be more evident at higher levels of thermal maturity). This is likely to result from intense shearing forces, suggesting that shock forces within basaltic material may produce more reactive carbon. This result has implications for potential (past) Martian habitability because impacted, reduced carbon may become more biologically accessible. The data presented suggest the RLS instrument will be able to characterise the contribution of impact shock within the landing site region, enhancing our ability to assess habitability.

The Complex Molecules Detector (CMOLD): A Fluidic-Based Instrument Suite to Search for (Bio)chemical Complexity on Mars and Icy Moons.

Organic chemistry is ubiquitous in the Solar System, and both Mars and a number of icy satellites of the outer Solar System show substantial promise for having hosted or hosting life. Here, we propose a novel astrobiologically focused instrument suite that could be included as scientific payload in future missions to Mars or the icy moons: the Complex Molecules Detector, or CMOLD. CMOLD is devoted to determining different levels of prebiotic/biotic chemical and structural targets following a chemically general approach (i.e., valid for both terrestrial and nonterrestrial life), as well as their compatibility with terrestrial life. CMOLD is based on a microfluidic block that distributes a liquid suspension sample to three instruments by using complementary technologies: (1) novel microscopic techniques for identifying ultrastructures and cell-like morphologies, (2) Raman spectroscopy for detecting universal intramolecular complexity that leads to biochemical functionality, and (3) bioaffinity-based systems (including antibodies and aptamers as capture probes) for finding life-related and nonlife-related molecular structures. We highlight our current developments to make this type of instruments flight-ready for upcoming Mars missions: the Raman spectrometer included in the science payload of the ESAs Rosalind Franklin rover (Raman Laser Spectrometer instrument) to be launched in 2022, and the biomarker detector that was included as payload in the NASA Icebreaker lander mission proposal (SOLID instrument). CMOLD is a robust solution that builds on the combination of three complementary, existing techniques to cover a wide spectrum of targets in the search for (bio)chemical complexity in the Solar System.

Design, development, and scientific performance of the Raman Laser Spectrometer EQM on the 2020 ExoMars (ESA) Mission

AbstractThe Raman Laser Spectrometer (RLS) is one of the three Pasteur Payload instruments located within the rover analytical laboratory drawer (ALD), for ESA's Aurora exploration programme, ExoMars 2020 mission. The instrument will analyse the crushed surface and subsurface samples that are positioned below the Raman optical head by the ALD carousel.The RLS engineering and qualification model (EQM) was delivered to ESA at the end of 2017, after a wide technical and scientific test characterization campaign. The scientific campaign comprised instrument calibration and detailed evaluation of the scientific requirements and overall performance. For spectral calibration, continuous emission standard lamps (such as Hg‐Ar, Ne, and Xe) were utilized, as well as Raman spectra of pure liquids typically used as standards (cyclohexane and carbon tetrachloride (CCl4)). In addition, Raman spectra of the RLS calibration target (CT), a small disc of polyethylene terephthalate (PET) were obtained at various temperatures. This target, placed inside the rover, will be used for both Instrument health checks and calibration activities throughout Mars operations. For the scientific requirements and performance evaluations, several liquid and solid samples were analysed under a wide range of ambient conditions. The obtained spectral band parameters (peak position, relative peak intensity, peak width, and peak profile) were evaluated. Also, the instrument response (in terms of SNR) was characterized at different integration times and detector operating temperatures. In this paper, we provide a description of the development, verification, functional test, and overall scientific performance of the RLS instrument developed for ExoMars. Particular attention is placed on the performance of the EQM, which is the most representative instrument, in terms of engineering and functionality, of the flight model (FM) and in addition is used for performing all the mechanical, thermal, and radiation tests necessary for space qualification (for planetary applications). The data presented and analysed here, comprise part of the overall dataset obtained during the full instrument characterization campaign conducted at INTA before and during delivery and integration of the EQM in the rover ALD at TAS‐I facilities (Torino, Italy). The results obtained confirm that the full functionality and scientific performance of the RLS instrument was maintained after integration.

Design of a Mars atmosphere simulation chamber and testing a Raman Laser Spectrometer (RLS) under conditions pertinent to Mars rover missions

Raman spectrometry is a powerful technique for the rapid identification of most minerals and organic chemicals without sample preparation. In this context, the European Space Agency (ESA) and NASA selected a Raman spectrometer in the payload of the future ExoMars and Mars 2020 missions to identify organic compounds and mineral products indicative of biological activity on Mars. Little is known, however, about the effects of Mars atmospheric conditions on instrument performance and on the Raman spectra. The objective of this study was to i) design and construct a versatile simulation chamber to reproduce the atmospheric conditions expected inside a rover on Mars, ii) to test the performance of a previously designed breadboard miniaturized Raman laser spectrometer (RLS) inside the chamber. The Mars Atmosphere Simulation Chamber (MASC) is a temperature and atmosphere controlled chamber. It includes an innovative heating-cooling system to create homogeneous temperatures inside the chamber that can be varied between 243 K and 283 K, while the charged coupled device (CCD) of the Raman spectrometer can be independently cooled (e.g., 233 K). A vacuum and gas control system permits evacuation of the chamber and the subsequent introduction of any (dried) gas mixture at partial pressures between 1 mbar and several bars. The minimum CCD temperature was found to depend on the surrounding MASC temperature and atmosphere. A vertical shift of 3 pixels on the CCD was observed for the Raman signals upon lowering the temperature from 283 to 253 K. We show that the RLS instrument gives reliable Raman spectra over the tested range of temperatures and from a vacuum of 4 x 10−5 mbar to a CO2 atmosphere at pressure relevant to Mars (8 mbar). For example, the Raman spectra of three test minerals, calcite, aragonite and baryte, showed identifiable Raman peaks with Raman shift values within ± 1 cm−1 of those reported in previous works under terrestrial conditions. This confirms that a RLS instrument is useful for the identification of minerals during future missions to Mars; once a necessary detector recalibration was carried out, the system performed well under 8 mbar pressure and 243 – 283 K. The MASC was found to be a versatile instrument; it can provide important information on instrument performance under Martian conditions and other temperatures and atmospheric conditions can also be simulated.

Analysis of the scientific capabilities of the ExoMars Raman Laser Spectrometer instrument

The Raman Laser Spectrometer (RLS) is part of the payload of the 2018 ExoMars rover. The Sample Preparation and Distribution System (SPDS) of the rover will crush samples acquired from down to two meters depth under the Martian surface, and provide them to the RLS instrument in the form of flattened powdered samples. The RLS instrument will acquire a minimum of 20 points on the flattened surface of the samples. To be able to obtain the maximum scientific return from the instrument once on Mars, a simulator of the SPDS system has been built to perform a series of experiments in a representative scenario. The crushing process implies the loss of rock structure and texture and, hence, the geological context of the samples. However, qualitative analysis with the RLS simulator on powdered natural samples and rocks showed that the RLS is capable of detecting carbonaceous material occurring in trace amounts in one of the rock samples (a silicified volcanic sand), more easily than with the same analysis on bulk. Furthermore, it is shown that minor phases in carbonate cements that cannot be detected by Raman in the bulk sample can be detected in the powder, thus allowing the identification of all the carbonate phases present in the cement crust. In order to quantify the detection threshold of the instrument, further analysis on controlled samples were performed. The results with the RLS SPDS simulator showed that the instrument can reach detection thresholds down to 1 % on powdered samples. Furthermore, analysis of controlled mixtures showed that performing a very simple intensity-based statistical analysis of the spectra can provide semi-quantification of the abundance of the mineral species with quite linear calibration curves.