ALBERT

Description: A wide diversity of planetary surfaces in the solar system represent high priority targets for in situ compositional and contextual analysis as part of future missions. The planned mission portfolio will inform our knowledge of the chemistry at play on Mars, icy moons, comets, and primitive asteroids, which can lead to advances in our understanding of the interplay between inorganic and organic building blocks that led to the evolution of habitable environments on Earth and beyond. In many of these environments, the presence of water or aqueously altered mineralogy is an important indicator of habitable environments that are present or may have been present in the past. As a result, the search for complex organic chemistry that may imply the presence of a feedstock, if not an inventory of biosignatures, is naturally aligned with targeted analyses of water-rich surface materials. Here we describe the two-step laser mass spectrometry (L2MS) analytical technique that has seen broad application in the study of organics in meteoritic samples, now demonstrated to be compatible with an in situ investigation with technique improvements to target high priority planetary environments as part of a future scientific payload. An ultraviolet (UV) pulsed laser is used in previous and current embodiments of laser desorption/ionization mass spectrometry (LDMS) to produce ionized species traceable to the mineral and organic composition of a planetary surface sample. L2MS, an advanced technique in laser mass spectrometry, is selective to the aromatic organic fraction of a complex sample, which can provide additional sensitivity and confidence in the detection of specific compound structures. Use of a compact two-step laser mass spectrometer prototype has been previously reported to provide specificity to key aromatic species, such as PAHs, nucleobases, and certain amino acids. Recent improvements in this technique have focused on the interaction between the mineral matrix and the organic analyte. The majority of planetary targets of astrobiological interest are characterized by the presence of water or hydrated mineral phases. Water signatures can indicate a history of available liquid water that may have played an important role in the chemical environment of these planetary surfaces and subsurfaces. The studies we report here investigate the influence of water content on the detectability of organics by L2MS in planetary analog samples.

Description: Since the Viking Program, quadrupole mass spectrometer (QMS) instruments have been used to explore a wide survey of planetary targets in our solar system, including (from the inner to outer reaches): Venus (Pioneer); our moon (LADEE); Mars (Viking, Phoenix, and Mars Science Laboratory); and, Saturns largest moon Titan (Cassini-Huygens). More recently, however, ion trap mass spectrometer (ITMS) instruments have found a niche as smaller, versatile alternatives to traditional quadrupole mass analyzers, capable of in situ characterization of planetary environments and the search for organic matter. For example, whereas typical QMS systems are limited to a mass range up to 500 Da and normally require multiple RF frequencies and pressures of less than 10(exp -6) mbar for optimal operation, ITMS instruments commonly reach upwards of 1000 Da or more on a single RF frequency, and function in higher pressure environments up to 10(exp -3) mbar.

Description: The identification of lunar resources such as water is a fundamental component of the the NASA Vision for Space Exploration. The Lunar Prospector mission detected high concentrations of hydrogen at the lunar poles that may indicate the presence of water or other volatiles in the lunar regolith [1]. One explanation for the presence of enhanced hydrogen in permanently shadowed crater regions is long term trapping of water-ice delivered by comets, asteroids, and other meteoritic material that have bombarded the Moon over the last 4 billion years [2]. It is also possible that the hydrogen signal at the lunar poles is due to hydrogen implanted by the solar wind which is delayed from diffusing out of the regolith by the cold temperatures [3]. Previous measurements of the lunar atmosphere by the LACE experiment on Apollo 17, suggested the presence of cold trapped vola'tiles that were expelled by solar heating [4]. In situ composition and isotopic analyses of the lunar regolith will be required to establish the abundance, origin, and distribution of water-ice and other volatiles at the lunar poles. Volatile Analysis by Pyrolysis of Regolith (VAPoR) on the Moon using mass spectrometry is one technique that should be considered. The VAPoR pyrolysis-mass spectrometer (pyr-MS) instrument concept study was selected for funding in 2007 by the NASA Lunar Sortie Science Opportunities (LSSO) Program. VAPoR is a miniature version of the Sample Analysis at Mars (SAM) instrument suite currently being developed at NASA Goddard for the 2009 Mars Science Laboratory mission (Fig. 1).

Description: Future landed missions to Mars will be guided by two strategic directions: (1) sample return to Earth, for comprehensive compositional analyses, as recommended by the 2011 NRC Planetary Decadal Survey; and (2) preparation for human exploration in the 2030s and beyond, as laid out by US space policy. The resultant mission architecture will likely require high-fidelity in situ chemical/organic sample analyses within an extremely constrained resource envelope. Both science goals (e.g., MEPAG Goal 1, return sample selection, etc.) as well as identification of any potential toxic and biological hazards to humans, must be addressed. Over the past several years of instrument development, we have found that the adaptable, compact, and highly capable technique of laser desorption/ionization time-of-flight mass spectrometry (LD-TOF-MS) has significant potential to contribute substantially to these dual objectives. This concept thus addresses Challenge Area 1: instrumentation and Investigation Approaches.

Description: Future surface missions to Mars and other planetary bodies will benefit from continued advances in miniature sensor and sample handling technologies that enable high-performance chemical analyses of natural samples. Fine-scale (approx.1 mm and below) analyses of rock surfaces and interiors, such as exposed on a drill core, will permit (1) the detection of habitability markers including complex organics in association with their original depositional environment, and (2) the characterization of successive layers and gradients that can reveal the time-evolution of those environments. In particular, if broad-based and highly-sensitive mass spectrometry techniques could be brought to such scales, the resulting planetary science capability would be truly powerful. The Linear Ion Trap Mass Spectrometer (LITMS) investigation is designed to conduct fine-scale organic and inorganic analyses of short (approx.5-10 cm) rock cores such as could be acquired by a planetary lander or rover arm-based drill. LITMS combines both pyrolysis/gas chromatograph mass spectrometry (GCMS) of sub-sampled core fines, and laser desorption mass spectrometry (LDMS) of the intact core surface, using a common mass analyzer, enhanced from the design used in the Mars Organic Molecule Analyzer (MOMA) instrument on the 2018 ExoMars rover. LITMS additionally features developments based on the Sample Analysis at Mars (SAM) investigation on MSL and recent NASA-funded prototype efforts in laser mass spectrometry, pyrolysis, and precision subsampling. LITMS brings these combined capabilities to achieve its four measurement objectives: (1) Organics: Broad Survey Detect organic molecules over a wide range of molecular weight, volatility, electronegativity, concentration, and host mineralogy. (2) Organic: Molecular Structure Characterize internal molecular structure to identify individual compounds, and reveal functionalization and processing. (3) Inorganic Host Environment Assess the local chemical/mineralogical makeup of organic host phases to help determine deposition and preservation factors. (4) Chemical Stratigraphy Analyze the fine spatial distribution and variation of key species with depth.

Description: Liquid chromatography mass spectrometry (LC-MS) is a well established laboratory technique for detecting and analyzing organic molecules. This approach has been especially fruitful in the analysis of nucleobases, amino acids, and establishing chirol ratios [1 -3]. We are developing OASIS, Organics Analyzer for Sampling Icy Surfaces, for future in situ landed missions to astrochemically important icy bodies, such as asteroids, comets, and icy moons. The OASIS design employs a microfabricated, on-chip analytical column to chromatographically separate liquid ana1ytes using known LC stationary phase chemistries. The elution products are then interfaced through electrospray ionization (ESI) and analyzed by a time-of-flight mass spectrometer (TOF-MS). A particular advantage of this design is its suitability for microgravity environments, such as for a primitive small body.

Description: Laser desorption/ionization time-of-flight mass spectrometry (LD-TOF-MS) is a versatile, low-complexity instrument class that holds significant promise for future landed in situ planetary missions that emphasize compositional analysis of surface materials. Here we describe a 5kg-class instrument that is capable of detecting and analyzing a variety of analytes directly from rock or ice samples. Through laboratory studies of a suite of representative samples, we show that detection and analysis of key mineral composition, small organics, and particularly, higher molecular weight organics are well suited to this instrument design. A mass range exceeding 100,000 Da has recently been demonstrated. We describe recent efforts in instrument prototype development and future directions that will enhance our analytical capabilities targeting organic mixtures on primitive and icy bodies. We present results on a series of standards, simulated mixtures, and meteoritic samples.

Description: The presentation examines the application of low reflectance surfaces in optical instruments, multi-walled carbon nanotubes (MWCNTs), research objects, MWCNT samples, measurement of 8 deg. directional/hemispherical reflectance, measurement of bidirectional reflectance distribution function (BRDF), and what is current the "blackest ever black".

Description: Measuring the chemical composition of planetary bodies and their atmospheres is key to understanding the formation of the Solar System and the evolution of the planets and their moons. In situ volatile measurements enable a ground-truth assessment of the distribution and abundance of resources such as water-ice and oxygen, important for a sustained human presence on the Moon and beyond. The Volatile Analysis by Pyrolysis of Regolith (VAPoR) instrument is a compact pyrolysis mass spectrometer designed to detect volatiles released from solid samples that are heated to elevated temperatures and is one technique that should be considered for resource prospecting on the Moon, Mars, and asteroids.