Adam Culka

Critical evaluation of a handheld Raman spectrometer with near infrared (785 nm) excitation for field identification of minerals

Handheld Raman spectrometers (Ahura First Defender XL, Inspector Raman DeltaNu) permit the recording of acceptable and good quality spectra of a large majority of minerals outdoors and on outcrops. Raman spectra of minerals in the current study were obtained using instruments equipped with 785 nm diode lasers. Repetitive measurements carried out under an identical instrumental setup confirmed the reliability of the tested Raman spectrometers. Raman bands are found at correct wavenumber positions within ±3 cm(-1) compared to reference values in the literature. Taking into account several limitations such as the spatial resolution and problems with metallic and black and green minerals handheld Raman spectrometers equipped with 785 nm diode lasers can be applied successfully for the detection of minerals from the majority of classes of the mineralogical system. For the detection of biomarkers and biomolecules using Raman spectroscopy, e.g. for exobiological applications, the near infrared excitation can be considered as a preferred excitation. Areas of potential applications of the actual instruments include all kind of common geoscience work outdoors. Modified Raman systems can be proposed for studies of superficial or subsurface targets for Mars or Lunar investigations.

Acquisition of Raman spectra of amino acids using portable instruments: Outdoor measurements and comparison

Raman spectra of 13 amino acids: L-alanine, β-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.

Using portable Raman spectrometers for the identification of organic compounds at low temperatures and high altitudes: exobiological applications

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°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.

The detection of biomarkers in evaporite matrices using a portable Raman instrument under Alpine conditions

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.

Testing a portable Raman instrument: The detection of biomarkers in gypsum powdered matrix under gypsum crystals

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.

Raman spectroscopic identification of arsenate minerals in situ at outcrops with handheld (532 nm, 785 nm) instruments.

Minerals are traditionally identified under field conditions by experienced mineralogists observing the basic physical properties of the samples. Under laboratory conditions, a plethora of techniques are commonly used for identification of the geological phases based on their structural and spectroscopic parameters. In this area, Raman spectrometry has become a useful tool to complement the more widely applied XRD. Today, however, there is an acute need for a technique for unambiguous in situ identification of minerals, within the geological as well as planetary/exobiology realms. With the potential for miniaturization, Raman spectroscopy can be viewed as a practical technique to achieve these goals. Here, for the first time, the successful application of handheld Raman spectrometers is demonstrated to detect and discriminate arsenic phases in the form of earthy aggregates. The Raman spectroscopic analyses of arsenate minerals were performed in situ using two handheld instruments, using 532 and 785 nm excitation. Bukovskýite, kaňkite, parascorodite, and scorodite were identified from Kaňk near Kutná Hora, CZE; kaňkite, scorodite, and zýkaite were identified at the Lehnschafter gallery in an old silver mine at Mikulov near Teplice, Bohemian Massif, CZE.

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.

The Ring Monstrance from the Loreto treasury in Prague: handheld Raman spectrometer for identification of gemstones

A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and unambiguous detection of common gemstones mounted in complex jewels. Here, complex religious artefacts and the Ring Monstrance from the Loreto treasury (Prague, Czech Republic; eighteenth century) were investigated. These discriminations are based on the very good correspondence of the wavenumbers of the strongest Raman bands of the minerals. Very short laser illumination times and efficient collection of scattered light were sufficient to obtain strong diagnostic Raman signals. The following minerals were documented: quartz and its varieties, beryl varieties (emerald), corundum varieties (sapphire), garnets (almandine, grossular), diamond as well as aragonite in pearls. Miniature Raman spectrometers can be recommended for common gemmological work as well as for mineralogical investigations of jewels and cultural heritage objects whenever the antiquities cannot be transported to a laboratory. This article is part of the themed issue ‘Raman spectroscopy in art and archaeology’.

Colonization of Snow by Microorganisms as Revealed Using Miniature Raman Spectrometers—Possibilities for Detecting Carotenoids of Psychrophiles on Mars?

We tested the potential of a miniaturized Raman spectrometer for use in field detection of snow algae pigments. A miniature Raman spectrometer, equipped with an excitation laser at 532 nm, allowed for the detection of carotenoids in cells of Chloromonas nivalis and Chlamydomonas nivalis at different stages of their life cycle. Astaxanthin, the major photoprotective pigment, was detected in algal blooms originating in snows at two alpine European sites that differed in altitude (Krkonoše Mts., Czech Republic, 1502 m a.s.l., and Ötztal Alps, Austria, 2790 m a.s.l.). Comparison is made with a common microalga exclusively producing astaxanthin (Haematococcus pluvialis). The handheld Raman spectrometer is a useful tool for fast and direct field estimations of the presence of carotenoids (mainly astaxanthin) within blooms of snow algae. Application of miniature Raman instruments as well as flight prototypes in areas where microbes are surviving under extreme conditions is an important stage in preparation for successful deployment of this kind of instrumentation in the framework of forthcoming astrobiological missions to Mars. Key Words: Snow algae-Chloromonas nivalis-Chlamydomonas nivalis-On-site field detection-Raman spectroscopy-Astaxanthin. Astrobiology 16, 913-924.

Raman and infrared spectroscopic study of boussingaultite and nickelboussingaultite

The Raman and infrared spectra of two secondary sulphate minerals, boussingaultite [(NH(4))(2)Mg(SO(4))(2) x 6 H(2)O] and nickelboussingaultite [(NH(4))(2)Ni,Mg(SO(4))(2) x 6 H(2)O] have been collected. Two bands observed at 983 and 990 cm(-1) were attributed to the nu(1)(SO(4)(2-)) symmetric stretching vibration. The bands at 1133, 1096 and 1063 cm(-1) in boussingaultite spectra and bands at 1149, 1093 and 1063 cm(-1) in nickelboussingaultite spectra were attributed to the nu(3)(SO(4)(2-)) antisymmetric stretching vibration. The splitting of the nu(4)(SO(4)(2-)) bending vibration produced bands at 625 and 615 cm(-1) in the boussingaultite spectra and 652, 624 and 602 cm(-1) in the nickelboussingaultite spectra. Similarly, in the case of the nu(2)(SO(4)) bending vibration, the bands were observed at 454 cm(-1) in the boussingaultite spectra and 482, 457 and 440 cm(-1) in the nickelboussingaultite spectra. The splitting of bands is the result of lowered symmetry of sulphate ions and possibly a result of substitution of Mg ions by Ni ions in nickelboussingaultite. The bands in the NH(4)(+) bending vibration region were observed at 1705 and 1678 cm(-1) (nu(2)), 1460 and 1438 cm(-1) (nu(4)) for the mineral boussingaultite. In the high wavenumber region the bands arising from the OH (bands above 3000 cm(-1)) and the NH(4)(+) (2940, 2918 and 2845 cm(-1)) stretching vibrations were identified.