RESUMEN

This study is primarily focused on proving the potential of miniaturized Raman systems to detect any biomolecular and mineral signal in natural geobiological samples that are relevant for future application of the technique within astrobiologically aimed missions on Mars. A series of evaporites of varying composition and origin from two extremely dry deserts were studied, namely Atacama and Mojave. The samples represent both dry evaporitic deposits and recent evaporitic efflorescences from hypersaline brines. The samples comprise halite and different types of sulfates and carbonates. The samples were analysed in two different ways: (i) directly as untreated rocks and (ii) as homogenized powders. Two excitation wavelengths of miniaturized Raman spectrometers were compared: 532 and 785 nm. The potential to detect carotenoids as biomarkers on Mars compared with the potential detection of carbonaceous matter using miniaturized instrumentation is discussed.

RESUMEN

The applications of analytical Raman spectroscopy in the characterisation of materials associated with archaeologically excavated artefacts, forensic investigations of drugs of abuse, security and crime scenes, minerals and rocks and future astrobiological space missions are now well established; however, these applications have emphasised the need for new developments in the area of miniaturised instrumentation which extends the concept and breadth of the analytical requirement to facilitate the provision of data from 'in field' studies. In this respect, the apparently unrelated themes of art and archaeology, forensic science, geological science and astrobiology as covered by this review are unified broadly by the ability to record data nondestructively and without resorting to sampling and the subsequent transfer of samples to the analytical laboratory. In studies of works of art there has long been a requirement for on-site analysis, especially for valuable paintings held under strict museum security and for wall paintings which cannot physically be removed from their setting; similarly, the use of portable Raman spectroscopy in archaeological and geological field work as a first-pass screening device which obviates the necessity of multiple and wasteful specimen collection is high on the wish-list of practicing spectroscopists. As a first-pass screening probe for forensic crime scenes, Raman spectroscopy has proved to be of inestimable value for the early detection of dangerous and prohibited materials such as drugs of abuse, explosives and their chemical precursors, and banned contraband biomaterials such as ivories and animal products; in these applications the advantage of the Raman spectroscopic technique for the recognition of spectral signatures from mixtures of inorganic and organic compounds is paramount and not afforded by other less portable instrumental techniques. Finally, in astrobiological work, these requirements also apply but with the additional prerequisite for system operation remotely - often over distances of several hundred million kilometres - as part of instrumental suites on robotic spacecraft and planetary landers; this necessitates robust and reliable instrumentation for the observation of unique and characteristic spectral features from the planetary geological surface and subsurface which are dependent on the assignment of both biological and geological band signatures.

RESUMEN

Laboratory cultures of a number of red extremely halophilic Archaea (Halobacterium salinarum strains NRC-1 and R1, Halorubrum sodomense, Haloarcula valismortis) and of Salinibacter ruber, a red extremely halophilic member of the Bacteria, have been investigated by Raman spectroscopy using 514.5nm excitation to characterize their carotenoids. The 50-carbon carotenoid α-bacterioruberin was detected as the major carotenoid in all archaeal strains. Raman spectroscopy also detected bacterioruberin as the main pigment in a red pellet of cells collected from a saltern crystallizer pond. Salinibacter contains the C40-carotenoid acyl glycoside salinixanthin (all-E, 2'S)-2'-hydroxy-1'-[6-O-(methyltetradecanoyl)-ß-d-glycopyranosyloxy]-3',4'-didehydro-1',2'-dihydro-ß,ψ-carotene-4-one), for which the Raman bands assignments of are given here for the first time.

Asunto(s)

RESUMEN

In this paper Raman spectra were obtained for a series of zeolites (thomsonite, stilbite, natrolite) and beryllium containing silicates (beryl, chrysoberyl, euclase, phenacite, bavenite, milarite) using a portable Raman specrometer with a 785 nm laser excitation to show the possibility to apply this setting for unambiguous detection and discrimination of these silicate minerals. Obtained spectra contain the most intense Raman bands at the same positions ±2-4 cm(-1) as reported in the literature. The use of these bands permits the unambiguous identification of these phases. Data show the possibility to discriminate individual species of similar whitish color and aspect. Measurements showed an excellent correspondence of Raman bands obtained using the portable system and a laboratory Raman microspectrometer (with the same excitation laser wavelenght). However, for several minerals of these groups (chrysoberyl, bertrandite, chiavennite) Raman spectra were not of sufficient quality to permit unambiguous identification. The reasons are discussed. Raman spectrum of chiavennite CaMnBe(2)Si(5)O(13)(OH)(2)·2(H(2)O) - a transformation product occurring together with bavenite on the surface of beryl crystals was obtained for the first time using the laboratory Raman spectrometer.

Asunto(s)

RESUMEN

In this study the possibility to detect biomarkers in experimentally prepared evaporitic matrices using a portable Raman instrument was estimated. Testing of the instrument was carried-out under the Alpine conditions outdoors at a low ambient temperature of -10 °C and at an altitude of 2860 m (Pitztal, Austria). Amino acids glycine and l-alanine, nucleo bases thymine and adenine, and metabolite urea were the organics mixed with gypsum powder. In this step it was shown that portable Raman spectroscopic instrumentation is capable of detecting biomarkers in complex samples in a host geological matrix. Such detection is possible even when the laser beam was focussed through the gypsum crystals 3-9 mm thick. For exobiology areas, this is an important fact, because life and/or related biomolecules are likely to be found in cavities under the surface of partially transparent evaporitic minerals that provide them a shelter from the hostile surrounding environment. For influencing the intensity of Raman bands the thickness of covering crystals is not as important as is the actual concentration of the biomarkers. This work and similar experiments serve for better evaluation of Raman spectroscopy as a method for future planetary exploration mission adoption.

Asunto(s)

RESUMEN

Recently, portable Raman instrumentation has been in demand for geosciences and for future planetary exploration for the identification of both organic and inorganic compounds in situ on Earth and on other planetary bodies, especially on Mars. Here we present the results of the analysis of halite/ß-carotene and halite/mellitic acid mixtures, performed by miniaturized Raman instrumentation equipped with 785 and 1064 nm excitation. Various proportions of organics in the halite matrix were examined. The lowest concentration of ß-carotene detected using the 785 nm laser was 1 mg kg(-1), with slightly better signals observed with shorter exposure times compared with the bench instrument using the same excitation wavelength. Mellitic acid was identified at the concentration level 10 g kg(-1). The 1064 nm excitation provided a lower sensitivity towards low concentration when compared with the 785 nm excitation.

Asunto(s)

RESUMEN

The detection of relatively low concentrations of the biomarkers in experimentally prepared evaporitic matrices using a portable Raman instrument (Ahura First Defender XL equipped with a 785 nm diode laser and fixed frontal probe) under Alpine conditions was tested. The instrument was able to detect nucleobases thymine (1673 and 984 cm(-1)) and adenine (722 and 536 cm(-1)) at concentrations of 1 wt% in the gypsum matrix outdoors at a low ambient temperature of -10°C and at an altitude of 2860 m(Pitztal, Austria). Amino acids glycine (1324 and 892 cm(-1)) and alanine (1357 and 851 cm(-1)) were unambiguously detected at 10 wt%. The main Raman features: strong, medium and partially weak intensity bands were observed in good agreement with the reference spectra for individual compounds (with a spectral resolution 7-10 cm(-1)) in the wavenumber range 200-1800 cm(-1). In the qualitative part of the experiment it was established that the portable instrument is able to detect the components in the mixture of three biomarkers (glycine, alanine and mellitic acid) and two evaporitic minerals unambiguously. It also detected the majority of the six similar amino acids in the mixture with gypsum and epsomite evaporitic minerals. The results obtained here demonstrate the possibility of a miniaturised Raman spectrometer to be able to cope with the various exobiologically related tasks that can be expected in the future planetary surface exploration missions. Within the payload designed by ESA and NASA for future missions, Raman spectroscopy will represent a unique research instrument.

Asunto(s)

RESUMEN

Raman spectra of 13 amino acids: L-alanine, ß-alanine, L-asparagine, L-aspartic acid, L-glutamic acid, L-glutamine, glycine, L-methionine, L-proline, L-serine, L-threonine, L-tryptophan and L-tyrosine were acquired outdoors using two portable Raman instruments from the Ahura and Delta Nu manufacturers, both with 785 nm laser excitation. Both instruments provide quality Raman spectra with nevertheless a variable dependence upon the prevailing experimental conditions. The data acquired in these experiments will inform the selection of suitable Raman spectrometers for the in-field detection of biomolecules of relevance to the search for life signatures spectroscopically in terrestrial extreme environments and in extraterrestrial exploration, especially of planetary surfaces and subsurfaces using robotic instrumentation.

Asunto(s)

RESUMEN

Organic minerals, organic acids and NH-containing organic molecules represent important target molecules for astrobiology. Here, we present the results of the evaluation of a portable hand-held Raman spectrometer to detect these organic compounds outdoors under field conditions. These measurements were carried out during the February-March 2009 winter period in Austrian Alpine sites at temperatures ranging between -5 and -25 degrees C. The compounds investigated were detected under field conditions and their main Raman spectral features were observed unambiguously at their correct reference wavenumber positions. The results obtained demonstrate that a miniaturized Raman spectrometer equipped with 785 nm excitation could be applied with advantage as a key instrument for investigating the presence of organic minerals, organic acids and nitrogen-containing organic compounds outdoors under terrestrial low-temperature conditions. Within the payload designed by ESA and NASA for several missions focusing on Mars, Titan, Europa and other extraterrestrial bodies, Raman spectroscopy can be proposed as an important non-destructive analytical tool for the in situ identification of organic compounds relevant to life detection on planetary and moon surfaces or near subsurfaces.

Asunto(s)

RESUMEN

The hyper-arid core of the Atacama Desert (Chile) is the driest place on Earth and is considered a close analogue to the extremely arid conditions on the surface of Mars. Microbial life is very rare in soils of this hyper-arid region, and autotrophic micro-organisms are virtually absent. Instead, photosynthetic micro-organisms have successfully colonized the interior of halite crusts, which are widespread in the Atacama Desert. These endoevaporitic colonies are an example of life that has adapted to the extreme dryness by colonizing the interior of rocks that provide enhanced moisture conditions. As such, these colonies represent a novel example of potential life on Mars. Here, we present non-destructive Raman spectroscopical identification of these colonies and their organic remnants. Spectral signatures revealed the presence of UV-protective biomolecules as well as light-harvesting pigments pointing to photosynthetic activity. Compounds of biogenic origin identified within these rocks differed depending on the origins of specimens from particular areas in the desert, with differing environmental conditions. Our results also demonstrate the capability of Raman spectroscopy to identify biomarkers within rocks that have a strong astrobiological potential.

Asunto(s)

RESUMEN

Raman spectral signatures have been obtained in situ for a series of minerals using portable Raman instruments. Cerussite, anglesite, wulfenite, titanite, calcite, tremolite, andradite and quartz were detected using portable Raman spectrometer First Defender XL (Ahura). Baryte, almandine and realgar Raman spectra obtained by this instrument in the field were compared to the data measured by the other mobile Raman instrument Inspector Raman (DeltaNu). Bench Raman dispersive microspectrometer (InVia Reflex, Renishaw) was used for comparative purposes. All spectra were obtained using a 785nm diode excitation. Although displaying lower spectral resolution comparing with the laboratory confocal instrument both portable instruments permit unambiguous detection of minerals in the field. These possibilities designate portable Raman machines as excellent tools for field geological applications. Miniaturised Raman instrument combined with LIBS will be included in the payload of the EXO Mars mission and would open interesting research possibilities in other in situ field planetary studies.

Asunto(s)

RESUMEN

As minerals, aromatic compounds occur very rarely in nature. Not more than 10 of such minerals are known and most of them were described in the coal deposits where they were formed as a result of coal bed fires or burning of coal waste heaps. Raman spectra of kladnoite C(6)H(4)(CO)(2)NH (natural phthalimide) and hoelite C(14)H(8)O(2), (natural 9,10-anthraquinone) display complex features. Raman microspectroscopy help to detect these phases non-destructively directly in the frame of rare samples. Investigated minerals are transformation products formed from gaseous phase originating in natural pyrolytical process occurring in the frame of coal heaps and coal series outcrops. It is recommended to include Raman spectroscopic characteristics of similar materials in databases for exobiological studies.

Asunto(s)

RESUMEN

Raman spectra have been obtained for crystals of the organic mineral mellite, from three different sites. Mellite occurs in the frame of the Tertiary series including lignite and coaly slates at Artern (Thuringia), Tula (Russia) and Bílina (Northern Bohemia). Mellite, Al(2)C(6)(COO)(6) x 16H(2)O, can be considered as evidence of previous biological activity in the geological record, similar to other salts of carboxylic acids such as whewellite and weddellite. Assignments of the major Raman features of mellite are proposed on the basis of comparison with the parent, mellitic acid, C(6)(COOH)(6). During diagenesis and epigenesis, mellite is formed from the reaction between organic carbon rich solutions with aluminosilicates, hence, with the current interest in the adoption of Raman spectroscopy for incorporation into robotic instrumentation for space mission landers, it is important that organic minerals be included into a spectroscopic database for the recognition of biomolecular signatures for remote life-detection experiments.

Asunto(s)

RESUMEN

In order to estimate the role of laminar flow of viscous, aromatic matter of carbonaceous precursor on microtextural preorientation in pregraphitization stage, we performed experiments with coal tar pitch (CTP). The principal hypothesis of preorientation of basic structural units (BSUs) in the case of laminar flow (pressure impregnation of CTP into porous matrix) and secondary release of volatiles during carbonization were studied. Glass microplates, planar porous medium with average distance between single microplates 5 microm were used as suitable porous matrix. Samples of CTP were carbonized up to 2500 degrees C. Optical microscopy reveals large flow domains in the sample of cokes carbonized between glass microplates. Raman microspectroscopy and high resolution transmission electron microscopy (HRTEM) show that at nanometric scale, the samples do not support the proposed hypotheses. With increasing temperature of pyrolysis, the graphitization of CTP impregnated into porous matrix proceeds to lower degree of structural ordering in comparison with single pyrolyzed CTP. This is explained by the release of volatile matter during carbonization in geometrically restricted spaces. More evident structural changes were discovered with the sample of single coke, where parts of fine grain mosaics, relicts of 'so called QI parts', reveal higher structural organization, in comparison with large and prolonged flow domains, similar to flow domains of cokes from microplates.

Asunto(s)