Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2016
A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and un... more 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 laborato...
The Science of the total environment, Jan 17, 2016
The mineralogical composition of mining wastes deposited in countless dumps around the world is t... more The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2wt.% As2O5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8wt...
In this study, Raman microspectrometry was tested as a nondestructive method of determining the l... more In this study, Raman microspectrometry was tested as a nondestructive method of determining the lowest detectable beta-carotene content in experimentally prepared evaporitic matrices (with respect to martian geology)- namely, gypsum, halite and epsomite.
We explored the use of Raman spectroscopy to simultaneously monitor the presence of different bio... more We explored the use of Raman spectroscopy to simultaneously monitor the presence of different biomarkers (carotenoids, elemental sulfur) within single cells of the purple sulfur photosynthetic bacteria Allochromatium vinosum and A. warmingii. Raman microspectrometry using excitation at 532 nm allowed the detection of different carotenoids. Raman signals of elemental sulfur appeared soon after feeding starved cells with sulfide. Raman spectroscopy is thus a convenient and sensitive technique to qualitatively and semiquantitatively assess the presence of different compounds of interest within single bacterial cells.
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
Raman spectroscopy has proved to be a very useful technique in astrobiology research. Especially,... more Raman spectroscopy has proved to be a very useful technique in astrobiology research. Especially, working with mobile instrumentation during fieldwork can provide useful experiences in this field. In this work, we provide an overview of some important aspects of this research and, apart from defining different types of mobile Raman spectrometers, we highlight different reasons for this research. These include gathering experience and testing of mobile instruments, the selection of target molecules and to develop optimal data processing techniques for the identification of the spectra. We also identify the analytical techniques that it would be most appropriate to combine with Raman spectroscopy to maximize the obtained information and the synergy that exists with Raman spectroscopy research in other research areas, such as archaeometry and forensics.
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
A prototype instrument, under development at the University of Leicester, for the future European... more 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 explo...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
The remote robotic exploration of extraterrestrial scenarios for evidence of biological colonizat... more 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 proces...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
In this paper, it is demonstrated how Raman spectroscopy can be used to detect different caroteno... more In this paper, it is demonstrated how Raman spectroscopy can be used to detect different carotenoids as possible biomarkers in various groups of microorganisms. The question which arose from previous studies concerns the level of unambiguity of discriminating carotenoids using common Raman microspectrometers. A series of laboratory-grown microorganisms of different taxonomic affiliation was investigated, such as halophilic heterotrophic bacteria, cyanobacteria, the anoxygenic phototrophs, the non-halophilic heterotrophs as well as eukaryotes (Ochrophyta, Rhodophyta and Chlorophyta). The data presented show that Raman spectroscopy is a suitable tool to assess the presence of carotenoids of these organisms in cultures. Comparison is made with the high-performance liquid chromatography approach of analysing pigments in extracts. Direct measurements on cultures provide fast and reliable identification of the pigments. Some of the carotenoids studied are proposed as tracers for halophile...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
This study is primarily focused on proving the potential of miniaturized Raman systems to detect ... more 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.
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
The hyper-arid core of the Atacama Desert (Chile) is the driest place on Earth and is considered ... more 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 r...
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
Organic minerals, organic acids and NH-containing organic molecules represent important target mo... more 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...
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
The characterization of minerals and biogeological deposits in a terrestrial Arabian sabkha has a... more The characterization of minerals and biogeological deposits in a terrestrial Arabian sabkha has a direct relevance for the exploration of Mars since the discovery by the NASA rovers Spirit and Opportunity of evaporate minerals on Mars that could have arisen from aquifers and subsurface water movement. The recognition of carbonates and sulphates in Gusev Crater has afforded an additional impetus to these studies, as relict or extant microbial extremophilic organisms could have colonized these geological matrices, as has been recorded on Earth. Here, we describe the Raman spectroscopic analysis of specimens of evaporitic materials sampled from the Dukhan sabkha, the largest inland sabkha in the Persian Gulf. With daily temperatures reaching in excess of 60 ° C and extreme salinity, we have identified the characteristic Raman signatures of key biomolecular compounds in association with evaporitic minerals and geological carbonate and sulphate matrices, which indicate that extremophilic...
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2016
A miniature lightweight portable Raman spectrometer and a palm-sized device allow for fast and un... more 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 laborato...
The Science of the total environment, Jan 17, 2016
The mineralogical composition of mining wastes deposited in countless dumps around the world is t... more The mineralogical composition of mining wastes deposited in countless dumps around the world is the key factor that controls retention and release of pollutants. Here we report a multi-method data set combining mineralogical (X-ray diffraction, electron microprobe and Raman microspectrometry) and geochemical (sequential extraction and pore water analysis) methods to resolve As mobility in two 50-years-old mining waste dumps. Originally, all of the As in the mining wastes selected for the study was present as arsenopyrite and with time it has been replaced by secondary As phases. At Jedová jáma mining area, the most of As precipitated as X-ray amorphous ferric arsenate (HFA). Arsenic is also accumulated in the scorodite and Fe (hydr)oxide (with up to 3.2wt.% As2O5) that is particularly represented by hematite. Mining wastes at Dlouhá Ves contain only trace amount of scorodite. Arsenic is primarily bound to Pb-jarosite and Fe (hydr)oxides (especially goethite) with up to 1.6 and 1.8wt...
In this study, Raman microspectrometry was tested as a nondestructive method of determining the l... more In this study, Raman microspectrometry was tested as a nondestructive method of determining the lowest detectable beta-carotene content in experimentally prepared evaporitic matrices (with respect to martian geology)- namely, gypsum, halite and epsomite.
We explored the use of Raman spectroscopy to simultaneously monitor the presence of different bio... more We explored the use of Raman spectroscopy to simultaneously monitor the presence of different biomarkers (carotenoids, elemental sulfur) within single cells of the purple sulfur photosynthetic bacteria Allochromatium vinosum and A. warmingii. Raman microspectrometry using excitation at 532 nm allowed the detection of different carotenoids. Raman signals of elemental sulfur appeared soon after feeding starved cells with sulfide. Raman spectroscopy is thus a convenient and sensitive technique to qualitatively and semiquantitatively assess the presence of different compounds of interest within single bacterial cells.
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
Raman spectroscopy has proved to be a very useful technique in astrobiology research. Especially,... more Raman spectroscopy has proved to be a very useful technique in astrobiology research. Especially, working with mobile instrumentation during fieldwork can provide useful experiences in this field. In this work, we provide an overview of some important aspects of this research and, apart from defining different types of mobile Raman spectrometers, we highlight different reasons for this research. These include gathering experience and testing of mobile instruments, the selection of target molecules and to develop optimal data processing techniques for the identification of the spectra. We also identify the analytical techniques that it would be most appropriate to combine with Raman spectroscopy to maximize the obtained information and the synergy that exists with Raman spectroscopy research in other research areas, such as archaeometry and forensics.
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
A prototype instrument, under development at the University of Leicester, for the future European... more 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 explo...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
The remote robotic exploration of extraterrestrial scenarios for evidence of biological colonizat... more 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 proces...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
In this paper, it is demonstrated how Raman spectroscopy can be used to detect different caroteno... more In this paper, it is demonstrated how Raman spectroscopy can be used to detect different carotenoids as possible biomarkers in various groups of microorganisms. The question which arose from previous studies concerns the level of unambiguity of discriminating carotenoids using common Raman microspectrometers. A series of laboratory-grown microorganisms of different taxonomic affiliation was investigated, such as halophilic heterotrophic bacteria, cyanobacteria, the anoxygenic phototrophs, the non-halophilic heterotrophs as well as eukaryotes (Ochrophyta, Rhodophyta and Chlorophyta). The data presented show that Raman spectroscopy is a suitable tool to assess the presence of carotenoids of these organisms in cultures. Comparison is made with the high-performance liquid chromatography approach of analysing pigments in extracts. Direct measurements on cultures provide fast and reliable identification of the pigments. Some of the carotenoids studied are proposed as tracers for halophile...
Philosophical transactions. Series A, Mathematical, physical, and engineering sciences, Jan 13, 2014
This study is primarily focused on proving the potential of miniaturized Raman systems to detect ... more 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.
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
The hyper-arid core of the Atacama Desert (Chile) is the driest place on Earth and is considered ... more 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 r...
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
Organic minerals, organic acids and NH-containing organic molecules represent important target mo... more 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...
Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2010
The characterization of minerals and biogeological deposits in a terrestrial Arabian sabkha has a... more The characterization of minerals and biogeological deposits in a terrestrial Arabian sabkha has a direct relevance for the exploration of Mars since the discovery by the NASA rovers Spirit and Opportunity of evaporate minerals on Mars that could have arisen from aquifers and subsurface water movement. The recognition of carbonates and sulphates in Gusev Crater has afforded an additional impetus to these studies, as relict or extant microbial extremophilic organisms could have colonized these geological matrices, as has been recorded on Earth. Here, we describe the Raman spectroscopic analysis of specimens of evaporitic materials sampled from the Dukhan sabkha, the largest inland sabkha in the Persian Gulf. With daily temperatures reaching in excess of 60 ° C and extreme salinity, we have identified the characteristic Raman signatures of key biomolecular compounds in association with evaporitic minerals and geological carbonate and sulphate matrices, which indicate that extremophilic...
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