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Miniature Mass Spectrometers on Space and Planetary Missions

Space flight mass spectrometers contribute our understanding of the origin and evolution of our solar system and even of life itself. This fundamental role has motivated increasing interest in miniature mass spectrometry for planetary missions. Several remarkable new instruments are en route or under development to investigate the composition of planetary bodies such as Mars and comets. For instance, the Sample Analysis at Mars (SAM) suite on the 2009 Mars Science Laboratory (MSL) mission includes a quadrupole mass spectrometer with a sophisticated gas processing system as well as pyrolysis and chemical derivatization protocols for solid samples. Future missions will require even lighter, lower power, and yet more capable mass spectrometers, particularly to analyze samples in situ on planetary surfaces. We have been developing laser-based mass spectrometers for elemental and organic/molecular analysis of rock, ice, or fine particle samples. These typically use time-of-flight (TOF) mass analyzers, which are readily miniaturized and can detect both atomic species and complex organics that occur in a variety of planetary materials. For example, nonvolatile polycyclic aromatic hydrocarbons and kerogen-like macromolecular carbon are found in some carbonaceous meteorites, which derived from asteroid parent bodies. A single focused laser pulse is able to volatilize and ionize some of these compounds for direct TOF analysis. While this is possible without any sample preparation or contact, sensitivity and quantitative performance can improve significantly with some sample handling. As such we have also been examining robotic mechanisms and protocols to accompany space flight mass spectrometers. In addition, sensors in early development may significantly improve these capabilities, via use of techniques such as switchable polarity, ambient pressure, or resonant ionization; tandem mass spectrometry (TOF or ion trap); and chemical imaging.

Brinckerhoff, William↗

Laser Ablation Electrodynamic Ion Funnel for In Situ Mass Spectrometry on Mars

A front-end instrument, the laser ablation ion funnel, was developed, which would ionize rock and soil samples in the ambient Martian atmosphere, and efficiently transport the product ions into a mass spectrometer for in situ analysis. Laser ablation creates elemental ions from a solid with a high-power pulse within ambient Mars atmospheric conditions. Ions are captured and focused with an ion funnel into a mass spectrometer for analysis. The electrodynamic ion funnel consists of a series of axially concentric ring-shaped electrodes whose inside diameters (IDs) decrease over the length of the funnel. DC potentials are applied to each electrode, producing a smooth potential slope along the axial direction. Two radio-frequency (RF) AC potentials, equal in amplitude and 180 out of phase, are applied alternately to the ring electrodes. This creates an effective potential barrier along the inner surface of the electrode stack. Ions entering the funnel drift axially under the influence of the DC potential while being restricted radially by the effective potential barrier created by the applied RF. The net result is to effectively focus the ions as they traverse the length of the funnel.

Johnson, Paul V.↗

Design and Demonstration of the Mars Organic Molecule Analyzer (MOMA) on the ExoMars 2018 Rover

The Mars Organic Molecule Analyzer (MOMA) investigation is a key astrobiology experiment scheduled to launch on the joint ESA-Roscosmos ExoMars 2018 rover mission. MOMA will examine the chemical composition of geological samples acquired from depths of up to two meters below the martian surface, where fragile organic molecules may be protected from destructive cosmic radiation and/or oxidative chemical reactions. The heart of the MOMA mass spectrometer subsystem (i.e., MOMA-MS) is a miniaturized linear ion trap (LIT) that supports two distinct modes of operation to detect: i) volatile and semi-volatile, low-to-moderate mass organics (less than or equal to 500 Da) via pyrolysis coupled with gas chromatography mass spectrometry (pyr/GCMS); and, ii) more refractory, moderate-to-high mass compounds (up to 1000 Da) via laser desorption (LDMS) at ambient Mars pressures. Additionally, the LIT mass analyzer enables selective ion trapping via multi-frequency waveform ion excitation (e.g., stored waveform inverse Fourier transform, or SWIFT), and structural characterization of complex molecules using tandem mass spectrometry (MSIMS). A high-fidelity Engineering Test Unit (ETU) of MOMAMS, including the LIT subassembly, dual-gun electron ionization source, micropirani pressure gauge, solenoid-driven aperture valve, redundant detection chains, and control electronics, has been built and tested at NASA GSFC under relevant operational conditions (pressure, temperature, etc.). Spaceflight qualifications of individual hardware components and integrated subassemblies have been validated through vibration, shock, thermal, lifetime, and performance evaluations. The ETU serves as a pathfinder for the flight model buildup, integration and test, as the ETU meets the form, fit and function of the flight unit that will be delivered to MPS in late 2015. To date, the ETU of MOMA-MS has been shown to meet or exceed all functional requirements, including mass range, resolution, accuracy, instrumental drift, and Iimit-of-detection specifications, thereby enabling the primary science objectives of the MOMA investigation and ExoMars 2018 mission.

Mars Organic Molecule Analyzer↗

Rocket- and aircraft-borne trace gas measurements in the winter polar stratosphere

In January and February 1987 stratospheric rocket- and aircraft-borne trace gas measurements were done in the North Polar region using ACIMS (Active Chemical Ionization Mass Spectrometry) and PACIMS (PAssive Chemical Ionization Mass Spectrometry) instruments. The rocket was launched at ESRANGE (European Sounding Rocket Launching Range) (68 N, 21 E, Northern Sweden) and the twin-jet research aircraft operated by the DFVLR (Deutsche Forschungs- und Versuchs-anstalt fuer Luft- und Raumfahrt), and equipped with a mass spectrometer laboratory was stationed at Kiruna airport. Various stratospheric trace gases were measured including nitric acid, sulfuric acid, non-methane hydrocarbons (acetone, hydrogen cyanide, acetonitrile, methanol etc.), and ambient cluster ions. The experimental data is presented and possible implications for polar stratospheric ozone discussed.

Arnold, F.↗

Instrumentation Working Group Summary

The Instrumentation Working Group compiled a summary of measurement techniques applicable to gas turbine engine aerosol precursors and particulates. An assessment was made of the limits, accuracy, applicability, and technology readiness of the various techniques. Despite advances made in emissions characterization of aircraft engines, uncertainties still exist in the mechanisms by which aerosols and particulates are produced in the near-field engine exhaust. To adequately assess current understanding of the formation of sulfuric acid aerosols in the exhaust plumes of gas turbine engines, measurements are required to determine the degree and importance of sulfur oxidation in the turbine and at the engine exit. Ideally, concentrations of all sulfur species would be acquired, with emphasis on SO2 and SO3. Numerous options exist for extractive and non-extractive measurement of SO2 at the engine exit, most of which are well developed. SO2 measurements should be performed first to place an upper bound on the percentage of SO2 oxidation. If extractive and non-extractive techniques indicate that a large amount of the fuel sulfur is not detected as SO2, then efforts are needed to improve techniques for SO3 measurements. Additional work will be required to account for the fuel sulfur in the engine exhaust. Chemical Ionization Mass Spectrometry (CI-MS) measurements need to be pursued, although a careful assessment needs to be made of the sampling line impact on the extracted sample composition. Efforts should also be placed on implementing non-intrusive techniques and extending their capabilities by maximizing exhaust coverage for line-of-sight measurements, as well as development of 2-D techniques, where feasible. Recommendations were made to continue engine exit and combustor measurements of particulates. Particulate measurements should include particle size distribution, mass fraction, hydration properties, and volatile fraction. However, methods to ensure that unaltered samples are obtained need to be developed. Particulate speciation was also assigned a high priority for quantifying the fractions of carbon soot, PAH, refractory materials, metals, sulfates, and nitrates. High priority was also placed on performing a comparison of particle sizing instruments. Concern was expressed by the workshop attendees who routinely make particulate measurements about the variation in number density measured during in-flight tests by different instruments. In some cases, measurements performed by different groups of researchers during the same flight tests showed an order of magnitude variation. Second priority was assigned to measuring concentrations of odd hydrogen and oxidizing species. Since OH, HO2, H2O2, and O are extremely reactive, non-extractive measurements are recommended. A combination of absorption and fluorescence is anticipated to be effective for OH measurements in the combustor and at the engine exit. Extractive measurements of HO2 have been made in the stratosphere, where the ambient level of OH is relatively low. Use of techniques that convert HO2 to OH for combustor and engine exit measurements needs to be evaluated, since the ratio of HO2/OH may be 1% or less at both the combustor and engine exit. CI-MS might be a viable option for H2O2, subject to sampling line conversion issues. However, H2O2 is a low priority oxidizing species in the combustor and at the engine exit. Two candidates for atomic oxygen measurements are Resonance Enhanced Multi-Photon Ionization (REMPI) and Laser-Induced Fluorescence (LIF). Particulate measurement by simultaneous extractive and non-extractive techniques was given equal priority to the oxidizer measurements. Concern was expressed over the ability of typical ground test sampling lines to deliver an unaltered sample to a remotely located instrument. It was suggested that the sampling probe and line losses be checked out by attempting measurements using an optical or non-extractive technique immediately upstream of the sampling probe. This is a possible application for Laser Induced Incandescence (LII) as a check on the volume fraction of soot. Optical measurements of size distribution are not well developed for ultrafine particles less than about 20 nm in diameter, so a non-extractive technique for particulate size distribution cannot be recommended without further development. Carbon dioxide measurements need to be made to complement other extractive measurement techniques. CO2 measurements enable conversion of other species concentrations to emission indices. Carbon monoxide, which acts as a sink for oxidizing species, should be measured using non-extractive techniques. CO can be rapidly converted to CO2 in extractive probes, and a comparison between extractive and non-extractive measurements should be performed. Development of non-extractive techniques would help to assess the degree of CO conversion, and might be needed to improve the concentration measurement accuracy. Measurements of NO(x) will continue to be critical due to the role of NO and NO2 in atmospheric chemistry, and their influence on atmospheric ozone. Time-resolved measurements of temperature, velocity, and species concentrations were included on the list of desired measurement. Thermocouples are typically adequate for engine exit measurements. PIV and LDV are well established for obtaining velocity profiles. The techniques are listed in the accompanying table; are divided into extractive and non-extractive techniques. Efforts were made to include a measurement uncertainty for each technique. An assessment of the technology readiness was included.

Zaller, Michelle↗