Evaluation of portable Raman instrumentation for identification of β-carotene and mellitic acid in two-component mixtures with halite

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/β-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 β-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.     

Analysis of thiols by microchip capillary electrophoresis for in situ planetary investigations

The detection of thiols on extraterrestrial bodies could provide evidence for life, as well as a host of potential prebiological or abiological processes. Here, we report a novel protocol to analyze organic thiols by microchip CE with LIF detection. Thiols were labeled with Pacific Blue C5 maleimide and analyzed by MEKC. The separation buffer consisted of 15 mM tetraborate pH 9.2 and 25 mM SDS. The optimized method provided LODs ranging from 1.4 to 15 nM. The method was validated using samples collected from geothermal pools at Hot Creek Gorge, California, which were found to contain 2‐propanethiol and 1‐butanethiol in the nanomolar concentration range. These samples serve as chemical analogues to material potentially present in the reducing environment of primitive Earth and also at sulfurous regions of Mars. Hence, the protocol developed here enables highly sensitive thiol analysis in samples with complexity comparable to that expected in astrobiologically relevant extraterrestrial settings. This new protocol could be readily added to the existing suite of microfluidic chemical analyses developed for in situ planetary exploration; all that is required is the incorporation of two new reagents to the payload of an existing instrument concept.     

质谱检测技术在火星探测中的应用

火星探测对人类寻找地外生命、探索行星产生和演化机制具有重要的科学意义.质谱技术已经在火星探测方面得到了实际应用,获得的数据正在改写着人类对火星的基本认识.本文综述了国内外质谱技术在火星探测任务中的应用现状,特别是我国学者的研究进展、存在问题和应对策略.     

地外样品研究中电子探针元素面扫描分析技术的应用

由于月壤等地外样品十分珍贵,在实验室研究中优先使用原位、微区、无损的元素分析方法。电子探针元素面扫描是地外样品研究中常用的分析方法之一。该方法可获取样品整体或者感兴趣区域的多种元素分布数据,应用于矿物相识别与含量估算,锆石等定年矿物的快速定位,矿物环带、出溶、反应边结构等特殊岩相和矿物接触关系等分析和研究。本研究中以嫦娥五号月壤、月球陨石、火星陨石研究为例,介绍了目前元素面扫描的应用方法。此外,本文还对比、分析了电子探针面扫描技术与其它面扫描技术的优缺点和适用范围。未来十年,我国将实施一系列月球、火星、小行星等天体采样返回任务。电子探针元素面扫描分析未来将在这些地外样品研究中广泛使用。同时,建议行星科学家围绕所关心的科学问题,合理搭配多种分析方法以实现各种技术优势互补和样品科学价值最大化,服务我国月球与深空探测任务科学产出和行星科学发展。     

Mass spectrometry in the U.S. space program: Past, present, and future

Recent years have witnessed significant progress on the miniaturization of mass spectrometers for a variety of field applications. This article describes the development and application of mass spectrometry (MS) instrumentation to support of goals of the U.S. space program. Its main focus is on the two most common space-related applications of MS: studying the composition of planetary atmospheres and monitoring air quality on manned space missions. Both sets of applications present special requirements in terms of analytical performance (sensitivity, selectivity, speed, etc.), logistical considerations (space, weight, and power requirements), and deployment in perhaps the harshest of all possible environments (space). The MS instruments deployed on the Pioneer Venus and Mars Viking Lander missions are reviewed for the purposes of illustrating the unique features of the sample introduction systems, mass analyzers, and vacuum systems, and for presenting their specifications which are impressive even by today's standards. The various approaches for monitoring volatile organic compounds (VOCs) in cabin atmospheres are also reviewed. In the past, ground-based GC/MS instruments have been used to identify and quantify VOCs in archival samples collected during the Mercury, Apollo, Skylab, Space Shuttle, and Mir missions. Some of the data from the more recent missions are provided to illustrate the composition data obtained and to underscore the need for instrumentation to perform such monitoring in situ. Lastly, the development of two emerging technologies, Direct Sampling Ion Trap Mass Spectrometry (DSITMS) and GC/Ion Mobility Spectrometry (GC/IMS), will be discussed to illustrate their potential utility for future missions.     

Gas chromatography in space.

Gas chromatography has proven to be a very useful analytical technique for in situ analysis of extraterrestrial environments as demonstrated by its successful operation on spacecraft missions to Mars and Venus. The technique is also one of the six scientific instruments aboard the Huygens probe to explore Titan's atmosphere and surface. A review of gas chromatography in previous space missions and some recent developments in the current environment of fiscal constraints and payload size limitations are presented.     

Raman spectroscopy in astrobiology

Raman spectroscopy is proposed as a valuable analytical technique for planetary exploration because it is sensitive to organic and inorganic compounds and able to unambiguously identify key spectral markers in a mixture of biological and geological components; furthermore, sample manipulation is not required and any size of sample can be studied without chemical or mechanical pretreatment. NASA and ESA are considering the adoption of miniaturised Raman spectrometers for inclusion in suites of analytical instrumentation to be placed on robotic landers on Mars in the near future to search for extinct or extant life signals. In this paper we review the advantages and limitations of Raman spectroscopy for the analysis of complex specimens with relevance to the detection of bio- and geomarkers in extremophilic organisms which are considered to be terrestrial analogues of possible extraterrestial life that could have developed on planetary surfaces.     

Investigation of biomolecules trapped in fluid inclusions inside halite crystals by Raman spectroscopy

Raman spectroscopy was tested for the identification of biomolecules (glycine, L-alanine, β-alanine, L-serine, and γ-aminobutyric acid) trapped in fluid inclusions inside halite model crystals. The investigated biomolecules represent important targets for future astrobiological missions. We know from terrestrial conditions that organic molecules and microorganisms can be sealed within fluid inclusions and can survive intact even for hundreds of millions of years. Raman spectroscopy is currently being miniaturized for future extraterrestrial planetary exploration (ExoMars 2018). Raman spectroscopy has shown the ability to detect investigated aminoacids nondestructively without any sample preparation, in short measurement times, and in relatively low concentrations. The number of registered Raman bands of investigated aminoacids and their intensity clearly correlate with the given concentration of biomolecules within fluid inclusions.     

Doubly-charged ions in the planetary ionospheres: a review

This paper presents a review of the current knowledge on the doubly-charged atomic and molecular positive ions in the planetary atmospheres of the Solar System. It is focused on the terrestrial planets which have a dense atmosphere of N(2) or CO(2), i.e. Venus, the Earth and Mars, but also includes Titan, the largest satellite of Saturn, which has a dense atmosphere composed mainly of N(2) and a few percent of methane. Given the composition of these neutral atmospheres, the following species are considered: C(++), N(++), O(++), CH(4)(++), CO(++), N(2)(++), NO(++), O(2)(++), Ar(++) and CO(2)(++). We first discuss the status of their detection in the atmospheres of planets. Then, we provide a comprehensive review of their complex and original photochemistry, production and loss processes. Synthesis tables are provided for those ions, while a discussion on individual species is also provided. Methods for detecting doubly-charged ions in planetary atmospheres are presented, namely with mass-spectrometry, remote sensing and fine plasma density measurements. A section covers some original applications, like the possible effect of the presence of doubly-charged ions on the escape of an atmosphere, which is a key topic of ongoing planetary exploration, related to the evolution of a planet. The results of models, displayed in a comparative way for Venus, Earth, Mars and Titan, are discussed, as they can predict the presence of doubly-charged ions and will certainly trigger new investigations. Finally we give our view concerning next steps, challenges and needs for future studies, hoping that new scientific results will be achieved in the coming years and feed the necessary interdisciplinary exchanges amongst different scientific communities.     

Laser-Induced Breakdown Spectroscopy for Mars surface analysis: capabilities at stand-off distances and detection of chlorine and sulfur elements

An international consortium is studying the feasibility of performing in situ geochemical analysis of Mars soils and rocks at stand-off distances up to several meters using the Laser-Induced Breakdown Spectroscopy (LIBS) technique. Stand-off analysis for Martian exploration imposes particular requirements on instrumentation, and it is necessary to first test the performance of such a system in the laboratory. In this paper, we test the capabilities of two different experimental setups. The first one is dedicated to the qualitative analysis of metals and rocks at distances between 3 and 12 m. With the second one, we have obtained quantitative results for aluminum alloys and developed a spectral database under Martian conditions for sulfur and chlorine, two elements that are geologically interesting but generally difficult to detect by LIBS under standard conditions (atmospheric pressure, close distance). These studies were carried out to determine an optimal instrumental design for in situ Mars analysis. The quality of analytical results affected by the optical elements and spectrometer has been particularly highlighted.     

Uranium(VI) transport through tri-n-butylphosphate kerosene oil liquid membrane supported in polypropylene film

Gamma-rays emitted from the surfaces of atmosphere-free extraterrestrial bodies such as asteroids, planets, or moons, can be measured to determine their chemical surface composition. Gamma-rays are emitted from naturally radioactive elements and, in their majority, are induced by the interaction of the energetic galactic cosmic particle radiation. Neutrons of the secondary hadron cascade contribute considerably to the gamma-ray line surface fluxes via nonelastic scattering and neutron-capture reactions. In principle, planetary gamma-ray spectroscopy resembles laboratory applications of prompt activation techniques. However, the evaluation of an orbital gamma-ray spectrum of other bodies than the Moon is difficult, as comparisons to so-called ground truth values, which functioned as standards, are not possible. Future planetary exploration missions will require the evaluation of recorded gamma-ray spectra without such standards. Therefore, in an attempt to overcome some of these difficulties, prompt gamma-ray spectra of planetary constituents were measured in a set of laboratory experiments with neutron-generator and cyclotron produced neutrons of energies up to 78 MeV. The significance of neutron-capture and nonelastic scattering gamma-ray lines for the characterization of major elements were established, and the application of the results to planetary gamma-ray spectroscopy of asteroids is discussed.     

Raman spectroscopic analysis of arctic nodules: relevance to the astrobiological exploration of Mars

The discovery of small, spherical nodules termed ‘blueberries’ in Gusev Crater on Mars, by the NASA rover Opportunity has given rise to much debate on account of their interesting and novel morphology. A terrestrial analogue in the form of spherical nodules of similar size and morphology has been analysed using Raman spectroscopy; the mineralogical composition has been determined and evidence found for the biological colonisation of these nodules from the spectral signatures of cyanobacterial protective biochemical residues such as scytonemin, carotenoids, phycocyanins and xanthophylls. This is an important result for the recognition of future sites for the planned astrobiological exploration of planetary surfaces using remote robotic instrumentation in the search for extinct and extant life biosignatures and for the expansion of putative terrestrial Mars analogue geological niches and morphologies.     

Miniaturized Laser-Induced Breakdown Spectroscopy for the in-situ analysis of the Martian surface: Calibration and quantification

We report on our ongoing studies to develop Laser-Induced Breakdown Spectroscopy (LIBS) for planetary surface missions to Mars and other planets and moons, like Jupiter's moon Europa or the Earth's moon. Since instruments for space missions are severely mass restricted, we are developing a light-weight miniaturized close-up LIBS instrument to be installed on a lander or rover for the in-situ geochemical analysis of planetary surface rocks and coarse fines. The total mass of the instrument will be ≈ 1 kg in flight configuration. Here we report on a systematic performance study of a LIBS instrument equipped with a prototype laser of 216 g total mass and an energy of 1.8 mJ. The LIBS measurements with the prototype laser and the comparative measurements with a regular 40 mJ laboratory laser were both performed under Martian atmospheric conditions.     

New trends in telescopic remote Raman spectroscopic instrumentation

Raman spectroscopy is a powerful analytical technique in many areas of research for several reasons. These include the sensitivity to small structural changes, non-invasive sampling capability, minimal sample preparation, narrow line widths of Raman lines, and high spatial resolution in the case of micro-Raman spectroscopy. Advancements in lasers, spectrographs and holographic optical components have made Raman spectroscopy an effective tool for analyzing natural and synthetic materials. These advances have led to the development of both in situ Raman spectroscopy and telescopic remote Raman spectroscopy for a lander or rover for planetary exploration. A telescopic Raman spectroscopic system capable of measuring Raman spectra of minerals, inorganic and organic chemicals, and biogenic materials to radial distances in the range 10-100 m has been developed. In this work, the author reviews the current status of telescopic remote Raman spectroscopic instrumentation and examines new trends in the field of remote Raman spectroscopy and its combination with time-resolved remote laser-induced native fluorescence (LINF) and laser-induced breakdown spectroscopy (LIBS), and their applications in earth and planetary science.     

Development of a temperature gradient focusing method for in situ extraterrestrial biomarker analysis

Scanning temperature gradient focusing (TGF) is a recently described technique for the simultaneous concentration and separation of charged analytes. It allows for high analyte peak capacities and low LODs in microcolumn electrophoretic separations. In this paper, we present the application of scanning TGF for chiral separations of amino acids. Using a mixture of seven carboxyfluorescein succinimidyl ester-labeled amino acids (including five chiral amino acids) which constitute the Mars7 standard, we show that scanning TGF is a very simple and efficient method for chiral separations. The modulation of TGF separation parameters (temperature window, pressure scan rate, temperature range, and chiral selector concentration) allows optimization of peak efficiencies and analyte resolutions. The use of hydroxypropyl-beta-CD at low concentration (1-5 mmol/L) as a chiral selector, with an appropriate pressure scan rate ( -0.25 Pa/s) and with a low temperature range (3-25 degrees C over 1 cm) provided high resolution between enantiomers (Rs >1.5 for each pair of enantiomers) using a short, 4 cm long capillary. With these new results, the scanning TGF method appears to be a viable method for in situ trace biomarker analysis for future missions to Mars or other solar system bodies.     

Life in the sabkha: Raman spectroscopy of halotrophic extremophiles of relevance to planetary exploration

The Raman spectroscopic biosignatures of halotrophic cyanobacterial extremophiles from sabkha evaporitic saltpans are reported for the first time and ideas about the possible survival strategies in operation have been forthcoming. The biochemicals produced by the cyanobacteria which colonise the interfaces between large plates of clear selenitic gypsum, halite, and dolomitized calcium carbonates in the centre of the salt pans are identifiably different from those which are produced by benthic cyanobacterial mats colonising the surface of the salt pan edges in the intertidal zone. The prediction that similar geological formations would have been present on early Mars and which could now be underlying the highly peroxidised regolith on the surface of the planet has been confirmed by recent satellite observations from Mars orbit and by localised traverses by robotic surface rovers. The successful adoption of miniaturised Raman spectroscopic instrumentation as part of a scientific package for detection of extant life or biomolecular traces of extinct life on proposed future Mars missions will depend critically on interpretation of data from terrestrial Mars analogues such as sabkhas, of which the current study is an example.     

Thermochemolysis in search for organics in extraterrestrial environments

It has been suggested that extraterrestrial organic material may well represent an important part of the organic material available for the origin of life. It may be expected that early life on Mars was similar to prokaryotic life on Earth and whatever preceded the prokaryotes. Detection of markers of microorganisms on Mars is then a key point in the search for life. The analytical technique has to be robust, sensitive and non-specific due to the large scope of targeted molecules. The main objective of this work is to present the capabilities of a TMAH-PY-GC–MS technique for the in situ analysis of organic matter in extraterrestrial soil samples. Two Martian analogues were analyzed to validate the technique. Biomarkers of microbial and higher plants origin such as lipids (n-alkenes, fatty acids) and carbohydrates were detected in samples. In the two samples, fatty acids had a microbial origin. On the other hand, n-alkenes and n-alkanols were from preserved higher plants biopolymers. TMAH-PY-GC–MS technique presented the advantage to wider the scopes of targeted molecules without adding additional device as pyrolysers are already used in spacecraft.     

Integrating amperometric detection with electrophoresis microchip devices for biochemical assays: recent developments

Recent advances in microfluidic systems, particularly in the Micro Total Analysis System (μTAS) or Lab On a Chip (LOC), drive the current analysis tools and equipment towards miniaturization, rapid at-line testing and mobility. The state-of-the-art microfluidic technology targets a wider range but smaller volumes of analytes, making the analytical procedure relatively easier and faster. This trend together with faster electronics and modern instrumentation systems will make real-time and in situ analysis a definite possibility. This review focuses on microchip capillary electrophoresis with amperometric detection (MCE-AD) for the detection of DNA and other electroactive analytes. The problems associated with the microchip design, in particular the choice of materials and the configuration of electrodes are discussed thoroughly and solutions are proposed. Significant developments in the related areas are also covered and reviewed critically.     

Aerogel: Space exploration applications

The unique physical properties of aerogel have proven to be enabling to a variety of both flight and proposed space exploration missions. The extremely low density and highly porous nature of aerogel makes it suitable for stopping high velocity particles, as a highly efficient thermal barrier, and as a porous medium for the containment of cryogenic fluids. The use of silica aerogel as a hypervelocity particle capture and return media for the Stardust Mission has drawn the attention of many in the space exploration community. Aerogel is currently being used as the thermal insulation material in the 2003 Mars Exploration Rovers. The SCIM (Sample Collection for the Investigation of Mars) and the STEP (Satellite Test of the Equivalence Principle) Missions are both proposed space exploration missions, in which, the use of aerogel is critical to their overall design and success. Composite materials comprised of silica aerogel and oxide powders are under development for use in a new generation of thermoelectric devices that are planned for use in many future space exploration mission designs. Work is currently ongoing in the development and production of non-silicate and composite aerogels to extend the range of useful applications envisioned for aerogel in future space exploration projects.     

Evaluation of a compact spectrograph for in-situ and stand-off Laser-Induced Breakdown Spectroscopy analyses of geological samples on Mars missions

Laser-induced Breakdown Spectroscopy (LIBS) is actively under development for future use on surface probes to Mars. The analytical method can be deployed for in-situ and/or stand-off analysis with the latter embodiment providing the greatest advantages compared to previous and current elemental analysis methods used for planetary surface analysis. For this application, LIBS must be thoroughly investigated in terms of analytical capabilities and flight-rated instruments must be developed. Because of the low pressure of the predominantly CO₂ atmosphere on Mars, studies are needed to understand analytical requirements and to determine performance under these conditions. Stand-off analysis demands the most stringent requirements on instrumentation. Therefore, it must be determined if the high performance components that are normally used in a typical LIBS laboratory setup, which are generally not optimized for small size and weight, are essential to obtain the maximum scientific return from a mission. A key component of a LIBS apparatus is the detection system consisting of a spectrograph and a detector. Here we present an evaluation of one design of a compact spectrograph (Ocean Optics HR2000) for in-situ and stand-off LIBS analyses of geological samples under Mars atmospheric conditions.