Richard Ingley

Raman spectroscopic analysis of geological and biogeological specimens of relevance to the ExoMars mission.

A novel miniaturized Raman spectrometer is scheduled to fly as part of the analytical instrumentation package on an ESA remote robotic lander in the ESA/Roscosmos ExoMars mission to search for evidence for extant or extinct life on Mars in 2018. The Raman spectrometer will be part of the first-pass analytical stage of the sampling procedure, following detailed surface examination by the PanCam scanning camera unit on the ExoMars rover vehicle. The requirements of the analytical protocol are stringent and critical; this study represents a laboratory blind interrogation of specimens that form a list of materials that are of relevance to martian exploration and at this stage simulates a test of current laboratory instrumentation to highlight the Raman technique strengths and possible weaknesses that may be encountered in practice on the martian surface and from which future studies could be formulated. In this preliminary exercise, some 10 samples that are considered terrestrial representatives of the mineralogy and possible biogeologically modified structures that may be identified on Mars have been examined with Raman spectroscopy, and conclusions have been drawn about the viability of the unambiguous spectral identification of biomolecular life signatures. It is concluded that the Raman spectroscopic technique does indeed demonstrate the capability to identify biomolecular signatures and the mineralogy in real-world terrestrial samples with a very high degree of success without any preconception being made about their origin and classification.

The ExoMars Raman spectrometer and the identification of biogeological spectroscopic signatures using a flight-like prototype

AbstractThe molecular specificity of Raman spectroscopy provides a powerful tool for the analytical interrogation of mineralogical and many biological specimens. The Raman Laser Spectrometer (RLS) is a compact Raman spectrometer under development for deployment on the Martian surface as part of the forthcoming ESA ExoMars mission. This will be the first Raman instrument deployed in space. The scientific interpretation of the data emerging from such an instrument not only addresses the geological and mineral composition of the specimens but also enables an assessment to be made of organic biomaterials that may be preserved in the planetary geological record. The latter evidence centres on the residual and distinctive chemistry relating to the biological adaptation of the geological matrix that has occurred as a result of extremophilic organisms colonizing suitable geological niches for their survival in environmentally stressed habitats on Mars. These biogeological modifications have been studied terrestrially for Mars analogue sites and consist of both a geological component and residual key organic biomarkers, the recognition of which would be a prime factor in life detection surveys of a planetary surface and subsurface. In this paper, the protocols required for the Raman spectral discrimination of key biogeological features that may be detectable on the Martian planetary surface or subsurface are developed using the UK breadboard (UKBB) instrument. This instrument has been constructed to be functionally equivalent to the RLS flight instrument design in order to evaluate the feasible science return of the instrument which will finally be delivered to Mars. Initial Raman measurements using the UKBB are presented and compared with the performance of a commercial laboratory Raman microscope. The initial measurements reported here demonstrate this flight-like prototype achieves straightforward detection of biological signatures contained in geological matrices with Raman band signal to noise ratios high enough to determine sample composition by inspection and without the need for deconvolution or further processing. FigureRaman excitation of sample at 532nm using commercial optical head.

Raman spectroscopy on Mars: identification of geological and bio-geological signatures in Martian analogues using miniaturized Raman spectrometers

The first Raman spectrometers to be used for in situ analysis of planetary material will be launched as part of powerful, rover-based analytical laboratories within the next 6 years. There are a number of significant challenges associated with building spectrometers for space applications, including limited volume, power and mass budgets, the need to operate in harsh environments and the need to operate independently and intelligently for long periods of time (due to communication limitations). Here, we give an overview of the technical capabilities of the Raman instruments planned for future planetary missions and give a review of the preparatory work being pursued to ensure that such instruments are operated successfully and optimally. This includes analysis of extremophile samples containing pigments associated with biological processes, synthetic materials which incorporate biological material within a mineral matrix, planetary analogues containing low levels of reduced carbon and samples coated with desert varnish that incorporate both geo-markers and biomarkers. We discuss the scientific importance of each sample type and the challenges using portable/flight-prototype instrumentation. We also report on technical development work undertaken to enable the next generation of Raman instruments to reach higher levels of sensitivity and operational efficiency.

Raman spectroscopy and the search for life signatures in the ExoMars Mission

The survival strategies of extremophilic organisms in terrestrially stressed locations and habitats are critically dependent on the production of protective chemicals in response to desiccation, low wavelength radiation insolation, temperature and the availability of nutrients. The adaptation of life to these harsh prevailing conditions involves the control of the substratal geology; the interaction between the rock and the organisms is critical and the biological modification of the geological matrix plays a very significant role in the overall survival strategy. Identification of these biological and biogeological chemical molecular signatures in the geological record is necessary for the recognition of the presence of extinct or extant life in terrestrial and extraterrestrial scenarios. Raman spectroscopic techniques have been identified as valuable instrumentation for the detection of life extra-terrestrially because of the use of non-invasive laser-based excitation of organic and inorganic molecules, and molecular ions with high discrimination characteristics; the interactions effected between biological organisms and their environments are detectable through the molecular entities produced at the interfaces, for which the vibrational spectroscopic band signatures are unique. A very important attribute of Raman spectroscopy is the acquisition of molecular experimental data non-destructively without the need for chemical or mechanical pre-treatment of the specimen; this has been a major factor in the proposal for the adoption of Raman instrumentation on robotic landers and rovers for planetary exploration, particularly for the forthcoming European Space Agency (ESA)/National Aeronautics and Space Administration (NASA) ExoMars mission. In this paper, the merits of using Raman spectroscopy for the recognition of key molecular biosignatures from several terrestrial extremophile specimens will be illustrated. The data and specimens used in this presentation have been acquired from Arctic and Antarctic cold deserts and a meteorite crater, from which it will be possible to assess spectral data relevant for the detection of extra-terrestrial extremophilic life signatures.

Biomarkers and their Raman spectroscopic signatures: a spectral challenge for analytical astrobiology

The remote robotic exploration of extraterrestrial scenarios for evidence of biological colonization in ‘search for life’ missions using Raman spectroscopy is critically dependent on two major factors: firstly, the Raman spectral recognition of characteristic biochemical spectral signatures in the presence of mineral matrix features; and secondly, the positive unambiguous identification of molecular biomaterials which are indicative of extinct or extant life. Both of these factors are considered here: the most important criterion is the clear definition of which biochemicals truly represent biomarkers, whose presence in the planetary geological record from an analytical astrobiological standpoint will unambiguously be indicative of life as recognized from its remote instrumental interrogation. Also discussed in this paper are chemical compounds which are associated with living systems, including biominerals, which may not in themselves be definitive signatures of life processes and origins but whose presence provides an indicator of potential life-bearing matrices.

Detection of reduced carbon in a basalt analogue for martian nakhlite: a signpost to habitat on Mars

C. W. Taylor and J. Still are thanked for skilled technical support. J. Parnell, H.G.M. Edwards, I. Hutchinson and R. Ingley acknowledge the support of the UKSA and the STFC Research Council in the UK ExoMars programme. L. V. Harris and S. McMahon acknowledge STFC studentship funding.

Detection of pigments of halophilic endoliths from gypsum: Raman portable instrument and European Space Agency's prototype analysis

A prototype instrument, under development at the University of Leicester, for the future European Space Agency (ESA) ExoMars mission, was used for the analysis of microbial pigments within a stratified gypsum crust from a hypersaline saltern evaporation pond at Eilat (Israel). Additionally, the same samples were analysed using a miniaturized Raman spectrometer, featuring the same 532 nm excitation. The differences in the position of the specific bands, attributed to carotenoid pigments from different coloured layers, were minor when analysed by the ESA prototype instrument; therefore, making it difficult to distinguish among the different pigments. The portable Delta Nu Advantage instrument allowed for the discrimination of microbial carotenoids from the orange/green and purple layers. The purpose of this study was to complement previous laboratory results with new data and experience with portable or handheld Raman systems, even with a dedicated prototype Raman system for the exploration of Mars. The latter is equipped with an excitation wavelength falling within the carotenoid polyene resonance region. The ESA prototype Raman instrument detected the carotenoid pigments (biomarkers) with ease, although further detailed distinctions among them were not achieved.

Biogeological Analysis of Desert Varnish Using Portable Raman Spectrometers

Desert varnishes are thin, dark mineral coatings found on some rocks in arid or semi-arid environments on Earth. Microorganisms may play an active role in their formation, which takes many hundreds of years. Their mineral matrix may facilitate the preservation of organic matter and is therefore of great relevance to martian exploration. Miniaturized Raman spectrometers (which allow nondestructive analysis of the molecular composition of a specimen) will equip rovers in forthcoming planetary exploration missions. In that context, and for the first time, portable Raman spectrometers operating in the green visible (532 nm as currently baselined for flight) and in the near-infrared (785 nm) were used in this study to investigate the composition (and substrate) of several samples of desert varnish. Rock samples that were suspected (and later confirmed) to be coated with desert varnish were recovered from two sites in the Mojave Desert, USA. The portable spectrometers were operated in flight-representative acquisition modes to identify the key molecular components of the varnish. The results demonstrate that the coatings typically comprise silicate minerals such as quartz, plagioclase feldspars, clays, ferric oxides, and hydroxides and that successful characterization of the samples can be achieved by using flightlike portable spectrometers for both the 532 and 785 nm excitation sources. In the context of searching for spectral signatures and identifying molecules that indicate the presence of extant and/or extinct life, we also report the detection of β-carotene in some of the samples. Analysis complications caused by the presence of rare earth element photoluminescence (which overlaps with and overwhelms the organic Raman signal when a 785 nm laser is employed) are also discussed.

Raman Spectral Signatures in the Biogeological Record: An Astrobiological Challenge

The application of Raman spectroscopic techniques to the characterisation of the protective biochemicals and their geological niche matrices used in the survival strategies of extremophilic organisms in terrestrially stressed environments (Wynn-Williams and Edwards, 2000a, b), coupled with the palaeogeological recognition that early Mars and Earth had maintained similar environments under which Archaean cyanobacteria could have developed3, has driven the acceptance of the proposal for the adoption of Raman spectroscopy as novel analytical instrumentation for planetary exploration (Edwards and Newton, 1999; Ellery and Wynn-Williams, 2003; Dickensheets et al., 2000). The European Space Agency (ESA) has announced that a miniaturised Raman spectrometer would form part of the Pasteur analytical life-detection protocol in the ExoMars-C mission for the search for traces of life on Mars in the Aurora programme to be launched as a joint two-rover mission with NASA in 2018. The Raman spectrometer will provide a key role in the first-pass analytical interrogation of powdered rock specimens from the Martian surface and subsurface aboard the ESA ExoMars-C rover vehicle.