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All sourcesNASA NTRSDOE OSTI
NASA NTRS2014

It's a Trap! A Review of MOMA and Other Ion Traps in Space or Under Development

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.

ion trap↗
NASA NTRS2011

A Dual Source Ion Trap Mass Spectrometer for the Mars Organic Molecule Analyzer of ExoMars 2018

We present details on the objectives, requirements, design and operational approach of the core mass spectrometer of the Mars Organic Molecule Analyzer (MOMA) investigation on the 2018 ExoMars mission. The MOMA mass spectrometer enables the investigation to fulfill its objective of analyzing the chemical composition of organic compounds in solid samples obtained from the near surface of Mars. Two methods of ionization are realized, associated with different modes of MOMA operation, in a single compact ion trap mass spectrometer. The stringent mass and power constraints of the mission have led to features such as low voltage and low frequency RF operation [1] and pulse counting detection.

Brickerhoff, William B.↗
NASA NTRS2018

A Low Cost Thermal Control Method for Testing in a Mars Environment

Due to the unique thermal vacuum testing requirements for a Mars Rover instrument, NASA Goddard developed a low cost, high fidelity thermal control system utilizing Thermal Electric Coolers (TECs) combined with a heat rejection fluid loop to actively control 8 independent payload thermal boundary zones in a simulated Mars pressure vacuum chamber with a Carbon Dioxide atmosphere. These zones could control instrument components to a specific temperature as a function of time to simulate exact temporal flight boundary predictions.The Mars Organic Molecule Analyzer (MOMA) instrument is a dual source (pyrolysis gas chromatograph and laser desorption) mass spectrometer (MS) based package that detects and characterizes organic molecules, as part of ESA's 2020 ExoMars Rover mission to seek the signs of life on Mars.Due to the unique thermal vacuum testing requirements for a Mars Rover instrument, NASA Goddard developed a low cost, high fidelity thermal control system utilizing Thermal Electric Coolers (TECs) combined with a heat rejection fluid loop to actively control 8 independent payload thermal boundary zones in a simulated Mars pressure vacuum chamber with a Carbon Dioxide atmosphere. These zones could control instrument components to a specific temperature as a function of time to simulate exact temporal flight boundary predictions.The Mars Organic Molecule Analyzer (MOMA) instrument is a dual source (pyrolysis gas chromatograph and laser desorption) mass spectrometer (MS) based package that detects and characterizes organic molecules, as part of ESA's 2020 ExoMars Rover mission to seek the signs of life on Mars.

MOMA↗
NASA NTRS2011

Operational Parameters, Considerations, and Design Decisions for Resource-Constrained Ion Trap Mass Spectrometers

Mass spectrometers are increasingly finding applications in new and unique areas, often in situations where key operational resources (i.e. power, weight and size) are limited. One such example is the Mars Organic Molecule Analyzer (MOMA). This instrument is a joint venture between NASA and the European Space Agency (ESA) to develop an ion trap mass spectrometer for chemical analysis on Mars. The constraints on such an instrument are significant as are the performance requirements. While the ideal operating parameters for an ion trap are generally well characterized, methods to maintain analytical performance with limited power and system weight need to be investigated and tested. Methods Experiments have been performed on two custom ion trap mass spectrometers developed as prototypes for the MOMA instrument. This hardware consists of quadrupole ion trap electrodes that are 70% the size of common commercial instrumentation. The trapping RF voltage is created with a custom tank circuit that can be tuned over a range of RF frequencies and is driven using laboratory supplies and amplifiers. The entire instrument is controlled with custom Lab VIEW software that allows a high degree of flexibility in the definition of the scan function defining the ion trap experiment. Ions are typically generated via an internal electron ionization source, however, a laser desorption source is also in development for analysis of larger intact molecules. Preliminary Data The main goals in this work have been to reduce the power required to generate the radio frequency trapping field used in an ion trap mass spectrometer. Generally minimizing the power will also reduce the volume and mass of the electronics to support the instrument. In order to achieve optimum performance, commercial instruments typically utilize RF frequencies in the 1 MHz range. Without much concern for power usage, they simply generate the voltage required to access the mass range of interest. In order to reduce the required RF voltage (and power), operation of the ion trap at lower RF frequencies has been investigated. Surprisingly, the performance of the instrument has only been slightly degraded at RF frequencies all the way down to 500 kHz. Mass resolution is relatively stable to this point and depending on the resonant ejection point used, the peak intensity is also quite stable. To date only masses up to m/z 200 have been fully investigated, however, additional studies are planned to verify the performance with higher mass ions. The lower frequency and voltage should reduce the pseudo potential well depth, eventually affecting the trapping efficiency of the instrument -- effect that could manifest itself in significantly limiting the mass range of trapped ions. Other methods to reduce the RF power while maintaining analytical performance are also under investigation. This includes ion ejection at lower q(sub z) values to access a given mass with a lower RF voltage. The loss of mass resolution at lower q(sub eject) points has been measured and current work is underway to leverage scan speed and the use of non-linear resonances in order to counter this trend. The overall trap performance under this range of operating conditions will be presented with a goal of identifying what trade-offs are acceptable.

Danell, Ryan M.↗
NASA NTRS2011

Development of a Low Power Gas Chromatograph-Mass Spectrometer for In-Situ Detection of Organics in Martian Soil

The Mars Organic Molecule Analyzer (MOMA) is a joint venture by NASA and the European Space Agency (ESA) to develop a sensitive, light-weight, low-power mass spectrometer for chemical analysis on Mars. MOMA is a key analytical instrument aboard the 2018 ExoMars rover mission seeking signs of past or present life. The current prototype was built to demonstrate operation of gas chromatography (OC) and laser desorption (LD) mass spectrometry under martian ambient conditions (5-7 Torr of CO2-rich atmosphere). Recent reports have discussed the MO MA concept, design and performance. Here, we update the current prototype performance, focusing specifically on the GCMS mode.

Pinnick, Veronica↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system has been guided by our under-standing of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure, and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-excesses of chiral amino acids or sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. However, studies of primitive meteorites have revealed that they contain extraterrestrial amino acids and sugar acids with large enantiomeric excesses (60% and higher) that resulted from non-biological processes [1], complicating the use of chiral asymmetry by itself as a definitive biosignature. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, is an objective of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks by the Sample Analysis at Mars (SAM) instrument suite on Mars [2-5], NASA’s Curiosity rover has found evidence of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars [5], indigenous achiral amino acids have been identified in one martian meteorite [6]. It is expected that amino acid racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [7]. The ESA/Roscosmos ExoMars mission scheduled for launch next year includes the Rosalind Franklin rover designed to acquire samples from a depth of ~2 m and deliver them to a suite of instruments, including the Mars Organic Molecule Analyzer (MOMA). The MOMA instrument contains a wet chemistry experiment designed specifically for the detection of amino acids and measurement of their enantiomeric compositions [8]. The complexity and limited duration of spaceflight operations, and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic com-pounds in ancient rocks, make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, bulk and molecule-specific isotopic, and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars derives from bio-tic or abiotic processes. Ultimately, Mars Sample Return of rock cores collected by NASA’s Perseverance rover may be our best chance of identifying chemical biosignatures, including any chiral amino acid asymmetry resulting from a past or present martian biota, if one ever existed on Mars. Here we review our current knowledge of the distributions, and enantiomeric and isotopic com-positions of amino acids found in meteorites compared to terrestrial biochemistry. We also propose a set of measurement criteria that should be used to help establish the sources of any amino acids detected in samples returned from Mars using state-of-the-art gas and liquid chromatography mass spectrometry techniques [1].

D P Glavin↗
NASA NTRS2008

Astrobiology Sample Analysis Program (ASAP) for Advanced Life Detection Instrumentation Development and Calibration

Scientific ground-truth measurements for near-term Mars missions, such as the 2009 Mars Science Laboratory (MSL) mission, are essential for validating current in situ flight instrumentation and for the development of advanced instrumentation technologies for life-detection missions over the next decade. The NASA Astrobiology Institute (NAI) has recently funded a consortium of researchers called the Astrobiology Sample Analysis Program (ASAP) to analyze an identical set of homogenized martian analog materials in a "round-robin" style using both state-of-the-art laboratory techniques as well as in-situ flight instrumentation including the SAM gas chromatograph mass spectrometer and CHEMIN X-ray diffraction/fluorescence instruments on MSL and the Urey and MOMA organic analyzer instruments under development for the 2013 ExoMars missions. The analog samples studied included an Atacama Desert soil from Chile, the Murchison meteorite, a gypsum sample from the 2007 AMASE Mars analog site, jarosite from Panoche Valley, CA, a hydrothermal sample from Rio Tinto, Spain, and a "blind" sample collected during the 2007 MSL slow-motion field test in New Mexico. Each sample was distributed to the team for analysis to: (1) determine the nature and inventory of organic compounds, (2) measure the bulk carbon and nitrogen isotopic composition, (3) investigate elemental abundances, mineralogy and matrix, and (4) search for biological activity. The experimental results obtained from the ASAP Mars analog research consortium will be used to build a framework for understanding the biogeochemistry of martian analogs, help calibrate current spaceflight instrumentation, and enhance the scientific return from upcoming missions.

Glavin, Daniel↗
NASA NTRS2011

Mass Spectrometry on Future Mars Landers

Mass spectrometry investigations on the 2011 Mars Science Laboratory (MSL) and the 2018 ExoMars missions will address core science objectives related to the potential habitability of their landing site environments and more generally the near-surface organic inventory of Mars. The analysis of complex solid samples by mass spectrometry is a well-known approach that can provide a broad and sensitive survey of organic and inorganic compounds as well as supportive data for mineralogical analysis. The science value of such compositional information is maximized when one appreciates the particular opportunities and limitations of in situ analysis with resource-constrained instrumentation in the context of a complete science payload and applied to materials found in a particular environment. The Sample Analysis at Mars (SAM) investigation on MSL and the Mars Organic Molecule Analyzer (MOMA) investigation on ExoMars will thus benefit from and inform broad-based analog field site work linked to the Mars environments where such analysis will occur.

Brinckerhoff, W. B.↗
NASA NTRS2012

Mass Spectrometers in Space!

Exploration of our solar system over several decades has benefitted greatly from the sensitive chemical analyses offered by spaceflight mass spectrometers. When dealing with an unknown environment, the broadband detection capabilities of mass analyzers have proven extremely valuable in determining the composition and thereby the basic nature of space environments, including the outer reaches of Earth s atmosphere, interplanetary space, the Moon, and the planets and their satellites. Numerous mass analyzer types, including quadrupole, monopole, sector, ion trap, and time-of-flight have been incorporated in flight instruments and delivered robotically to a variety of planetary environments. All such instruments went through a rigorous process of application-specific development, often including significant miniaturization, testing, and qualification for the space environment. Upcoming missions to Mars and opportunities for missions to Venus, Europa, Saturn, Titan, asteroids, and comets provide new challenges for flight mass spectrometers that push to state of the art in fundamental analytical technique. The Sample Analysis at Mars (SAM) investigation on the recently-launch Mars Science Laboratory (MSL) rover mission incorporates a quadrupole analyzer to support direct evolved gas as well as gas chromatograph-based analysis of martian rocks and atmosphere, seeking signs of a past or present habitable environment. A next-generation linear ion trap mass spectrometer, using both electron impact and laser ionization, is being incorporated into the Mars Organic Molecule Analyzer (MOMA) instrument, which will be flown to Mars in 2018. These and other mass spectrometers and mission concepts at various stages of development will be described.

Brinckerhoff, William B.↗
NASA NTRS2014

Development of a Linear Ion Trap Mass Spectrometer (LITMS) Investigation for Future Planetary Surface Missions

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.

Mars↗
NASA NTRS2018

A Novel Multi-Spacecraft Interplanetary Global Trajectory Optimization Transcription

As the frontier of space exploration continues to advance, so does the design complexity of future interplanetary missions. One avenue of this increasing complexity includes a class of designs known as "Distributed Spacecraft Missions"; missions where multiple spacecraft coordinate to perform shared objectives. Current approaches for the global trajectory optimization of these Multi-Vehicle Missions (MVMs) are prone to shortcomings including laborious iterative design, considerable human-in-the-loop effort, treatment of the multi-vehicle problem as multiple separate trajectory optimization subproblems (resulting in suboptimal solutions where the whole is less than the sum of its parts), and poor handling of coordination objectives and constraints. There are only a handful of software platforms in existence capable of fully-automated, rapid, interplanetary mission and systems global optimization including the Parallel Global Multiobjective Optimizer (PaGMO), the Gravity Assisted Low-thrust Local Optimization Program (GALLOP), and the Evolutionary Mission Trajectory Generator (EMTG). However, none of these tools is capable of performing such tasks for MVM designs. The work outlined in this paper lays the groundwork for a technique to begin addressing these shortcomings. We present a fully-automated technique which frames interplanetary MVMs as Multi-Objective, Multi-Agent Hybrid Optimal Control Problems (MOMA HOCP). First, the basic functionality of this technique is validated on the single-vehicle problem of reproducing the Cassini interplanetary cruise.

Interplanetary↗
NASA NTRS2018

A Novel Multi-Spacecraft Interplanetary Global Trajectory Optimization Transcription

As the frontier of space exploration continues to advance, so does the design complexity of future interplanetary missions. One avenue of this increasing complexity includes a class of designs known as ``Distributed Spacecraft Missions"; missions where multiple spacecraft coordinate to perform shared objectives. Current approaches for the global trajectory optimization of these Multi-Vehicle Missions (MVMs) are prone to shortcomings including laborious iterative design, considerable human-in-the-loop effort, treatment of the multi-vehicle problem as multiple separate trajectory optimization subproblems (resulting in suboptimal solutions where the whole is less than the sum of its parts), and poor handling of coordination objectives and constraints. There are only a handful of software platforms in existence capable of fully-automated, rapid, interplanetary mission and systems global optimization including the Parallel Global Multiobjective Optimizer (PaGMO), the Gravity Assisted Low-thrust Local Optimization Program (GALLOP), and the Evolutionary Mission Trajectory Generator (EMTG). However, none of these tools is capable of performing such tasks for MVM designs. The work outlined in this paper lays the groundwork for a technique to begin addressing these shortcomings. We present a fully-automated technique which frames interplanetary MVMs as Multi-Objective, Multi-Agent Hybrid Optimal Control Problems (MOMA HOCP). First, the basic functionality of this technique is validated on the single-vehicle problem of reproducing the Cassini interplanetary cruise.

Napier, Sean W.↗
NASA NTRSDate not supplied

The Search for Chiral Asymmetry as a Potential Biosignature in Samples from Mars

The search for evidence of extraterrestrial life in our solar system is currently guided by our understanding of terrestrial biology and its associated biosignatures. The observed homochirality in all life on Earth, that is, the predominance of “left-handed” or L-amino acids and “right-handed” or D-sugars, is a unique property of life that is crucial for molecular recognition, enzymatic function, information storage and structure and is thought to be a prerequisite for the origin or early evolution of life. Therefore, the detection of L- or D-enantiomeric excesses of chiral amino acids and sugars could be a powerful indicator of extant or extinct life on Mars or other habitable environments in our solar system. The exploration of habitable environments on Mars, including an assessment of the preservation potential for complex organics of either abiotic or biological origin, remains a key goal of both current and future Mars missions. Now with the unambiguous detection of indigenous organic matter in sedimentary rocks on Mars [1-3], NASA’s Curiosity rover has significantly advanced our understanding of the preservation of potential chemical biosignatures in the martian near surface. Although amino acids have not yet been identified by in situ measurements on Mars, if they were present, it is expected that amino acid hydrolysis and racemization would be very slow and any chiral or isotopic signatures from an extinct martian biota could be preserved for billions of years, given the extremely cold and dry surface conditions [4]. One of ESA’s Rosalind Franklin rover payload instruments called the Mars Organic Molecule Analyzer (MOMA) includes a wet chemistry package capable of measuring the enantiomeric ratios of any chiral amino acids present at part-per-million concentrations or higher [5]. The complexity and limited duration of spaceflight operations and the known analytical challenges associated with in situ extraction and characterization of trace reduced organic compounds in ancient rocks make it challenging to determine the origins of martian organic matter found to date. Coordinated state-of-the-art laboratory measurements of returned samples from Mars that include spatially resolved chemical, mineralogical, and isotopic studies and molecule-specific isotopic and enantiomeric measurements will be required to firmly establish whether the complex organic matter detected on Mars comes from biotic or abiotic sources. Ultimately, sample return may be our best chance of identifying chemical biosignatures from a past or present martian biota, if one ever existed on Mars. NASA’s Perseverance rover will collect dozens of surface sample cores for possible future return to Earth by NASA and ESA. Here we review our current knowledge of the distributions and enantiomeric and isotopic compositions of non-biological amino acids found in meteorites compared to terrestrial biochemistry and propose a set of measurement criteria that should be used to help establish the origin of any chiral asymmetry detected in samples from Mars [6].

Daniel P Glavin↗
NASA NTRSDate not supplied

The ARADS Project as an Astrobiological Survey Mission Prototype

An astrobiological survey prior to human arrival will be important for preservation of signs of any existing or past evidence of Martian life, to reduce the risk of unintentional forward contamination of Martian environments in which terrestrial microbes might be able to gain a foothold (e.g., [1]), and to potentially protect the health of any human crews and enable their safe return to Earth. Evaluating for the presence of life and biosignatures may become a critical-path Mars exploration precursor in the not-so-far future, circa 2030-35. The near-subsurface, with its potential combination of volatiles, vapor exchange with the surface, and shelter from surface radiation, will be a primary initial target for in-situ astrobiological investigation. Sample acquisition, drilling and sample handling are key elements of robotic missions that target the subsurface [2], as well as near-surface ground ice deposits. In the mid 2000s, the Mars Astrobiology Field Laboratory (AFL) was proposed as a follow-on mission concept to the Mars Science Laboratory (MSL)/Curiosity rover mission [3]. The AFL would have included precision drilling to 2m, automated sample handling and remote processing of cores. However, the AFL concept needed further development and maturation. The Atacama Rover Astrobiology Drilling Studies (ARADS) project concept [4] was in part AFL-inspired. The 2014 ARADS concept included a medium sized rover, with habitability instruments, including the Phoenix Wet Chemistry Laboratory (WCL) [5], and an enhanced version of the ExoMars Mars Organic Molecule Analyzer (MOMA) Laser Desorption-Linear Ion Trap Mass Spectrometer (LITMS) [6]. ARADS likewise included two biosignature detection instruments -- the Signs of Life Detector (SOLID) immunoassay instrument [7,8] and the Chemical Laptop-derived [9] Planetary In-Situ Capillary Electrophoresis System (PISCES), while mitigating Planetary Protection-relevant contamination issues [10]. ARADS project objectives were to demonstrate the potential science return for such a mission in the context of the search for evidence of life, and technically to demonstrate the feasibility of roving with drilling missions to Mars. ARADS technology goals targeted analog-site demonstrations of automated drilling and sampling, integrated with its mobile habitability and biosignature detection instruments. And ARADS science operations goals developed remote science, contamination mitigation, and communications methods to enable simulating AFL-like science operations with time delays, directed by a remote science team[11]. Five subsequent Mars analog site field demonstrations (in Chile’s hyperarid Atacama Desert, 2016-19) provided a step-by-step development pathway for the ARADS platform’s science capabilities and systems integration, culminating in an integrated remote roving mission simulation in the final ARADS year (2019).

biosignatures↗
DOE OSTI2025

Action painting under spectroscopic light: Excited-state exchange interactions behind the vibrant blue in Jackson Pollock’s Number 1A, 1948

Number 1A, 1948 by Jackson Pollock is a quintessential example of his action painting technique where ropes of color, drips of black, and pools of white coalesce into the layered dynamism that defines his style. While past work has identified the red and yellow pigments that form part of his core palette, the vibrant blue in the painting has remained unassigned. In this study resonance Raman spectroscopy is used to assign the blue in the painting as manganese blue. This assignment offers critical context for the conservation of his works. Importantly, assignment of this pigment enables spectroscopic investigation of the electronic structure origin of the pure hue of manganese blue and the chemical phenomena that produce its color. To probe these phenomena, resonance Raman data are coupled to magnetic circular dichroism spectroscopy and density functional theory calculations to assign and analyze the two electronic transitions that create the blue color. This study reveals these bands are split by excited-state exchange interactions; the gap between them contains the reflected light that gives manganese blue its appearance. This sheds light on distinct advantages of molecular inorganic pigments: their ability to leverage ligand field effects in charge transfer states to create multiple intense visible absorption features and the ability to fine-tune pigment color through host lattice electrostatics.

DFT↗