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At least 73 records · Page 4

Compact Two-step Laser Time-of-Flight Mass Spectrometer for in Situ Analyses of Aromatic Organics on Planetary Missions

RATIONALE A miniature time-of-flight mass spectrometer has been adapted to demonstrate two-step laser desorption-ionization (LOI) in a compact instrument package for enhanced organics detection. Two-step LDI decouples the desorption and ionization processes, relative to traditional laser ionization-desorption, in order to produce low-fragmentation conditions for complex organic analytes. Tuning UV ionization laser energy allowed control ofthe degree of fragmentation, which may enable better identification of constituent species. METHODS A reflectron time-of-flight mass spectrometer prototype measuring 20 cm in length was adapted to a two-laser configuration, with IR (1064 nm) desorption followed by UV (266 nm) postionization. A relatively low ion extraction voltage of 5 kV was applied at the sample inlet. Instrument capabilities and performance were demonstrated with analysis of a model polycyclic aromatic hydrocarbon, representing a class of compounds important to the fields of Earth and planetary science. RESULTS L2MS analysis of a model PAH standard, pyrene, has been demonstrated, including parent mass identification and the onset o(tunable fragmentation as a function of ionizing laser energy. Mass resolution m/llm = 380 at full width at half-maximum was achieved which is notable for gas-phase ionization of desorbed neutrals in a highly-compact mass analyzer. CONCLUSIONS Achieving two-step laser mass spectrometry (L2MS) in a highly-miniature instrument enables a powerful approach to the detection and characterization of aromatic organics in remote terrestrial and planetary applications. Tunable detection of parent and fragment ions with high mass resolution, diagnostic of molecular structure, is possible on such a compact L2MS instrument. Selectivity of L2MS against low-mass inorganic salt interferences is a key advantage when working with unprocessed, natural samples, and a mechanism for the observed selectivity is presented.

Getty, Stephanie↗

A Cerenkov - Delta E/Delta X experiment for measuring cosmic-ray isotopes from neon through iron

Cosmic-ray isotope masses are measured in a balloon-borne cosmic-ray experiment. Two Cerenkov counters and an NaI scintillator stack are used to determine changes in energy and in the Lorentz factor for a traversing or stopping particle. The mass is defined at the ratio of the change in energy to the change in the Lorentz factor. For incident elements from neon through iron, mass resolution better than 0.3 a.m.u. is expected, with incident Lorentz gammas ranging from 2.4 to 3.1, depending on the element. The mass resolution is approximately 0.2 a.m.u., measured for Mn-55 ions having an incident Lorentz factor of 2.75.

Buffington, A.↗

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.↗

New high-resolution electrostatic ion mass analyzer using time of flight

The design of a high-resolution ion-mass analyzer is described, which is based on an accurate measurement of the time of flight (TOF) of ions within a region configured to produce a harmonic potential. In this device, the TOF, which is independent of ion energy, is determined from a start pulse from secondary electrons produced when the ion passes through a thin carbon foil at the entrance of the TOF region and at a stop pulse from the ion striking a microchannel plate upon exciting the region. A laboratory prototype instrument called 'VMASS' was built and was tested at the Goddard Space Flight Center electrostatic accelerator, showing a good mass resolution of the instrument. Sensors of the VMASS type will form part of the WIND Solar Wind and Suprathermal Ion experiment, the Soho mission, and the Advanced Composition Explorer.

Hamilton, D. C.↗

Observing Planets and Small Bodies in Sputtered High Energy Atom (SHEA) Fluxes

The evolution of the surfaces of bodies unprotected by either strong magnetic fields or thick atmospheres in the Solar System is caused by various processes, induced by photons, energetic ions and micrometeoroids. Among these processes, the continuous bombardment of the solar wind or energetic magnetospheric ions onto the bodies may significantly affect their surfaces, with implications for their evolution. Ion precipitation produces neutral atom releases into the exosphere through ion sputtering, with velocity distribution extending well above the particle escape limits. We refer to this component of the surface ejecta as sputtered high-energy atoms (SHEA). The use of ion sputtering emission for studying the interaction of exposed bodies (EB) with ion environments is described here. Remote sensing in SHEA in the vicinity of EB can provide mapping of the bodies exposed to ion sputtering action with temporal and mass resolution. This paper speculates on the possibility of performing remote sensing of exposed bodies using SHEA The evolution of the surfaces of bodies unprotected by either strong magnetic fields or thick atmospheres in the Solar System is caused by various processes, induced by photons, energetic ions and micrometeoroids. Among these processes, the continuous bombardment of the solar wind or energetic magnetospheric ions onto the bodies may significantly affect their surfaces, with implications for their evolution. Ion precipitation produces neutral atom releases into the exosphere through ion sputtering, with velocity distribution extending well above the particle escape limits. We refer to this component of the surface ejecta as sputtered high-energy atoms (SHEA). The use of ion sputtering emission for studying the interaction of exposed bodies (EB) with ion environments is described here. Remote sensing in SHEA in the vicinity of EB can provide mapping of the bodies exposed to ion sputtering action with temporal and mass resolution. This paper speculates on the possibility of performing remote sensing of exposed bodies using SHEA and suggests the need for quantitative results from laboratory simulations and molecular physic modeling in order to understand SHEA data from planetary missions. In the Appendix, referenced computer simulations using existing sputtering data are reviewed.

Milillo, A.↗

The Combined Detection of Morphological and Molecular Biomarkers: Implications for Astrobiology

Experience gathered by previous researchers during their hunt for evidence of early Earth life has shown the complexity in interpreting observations of possible microfossils and to establish the evidence to be positive. Similarly, the stillsimmering controversy on the nature of the nano-structures in Martian meteorite ALH84001 described by McKay et al. (1996) emphasizes the difficulties of conclusively identifying those structures as (a) fossilized bacterial cells and (b) establish their indigeneity. A better understanding of biological signatures in rocks is needed in order to identify traces of microbial life, which include morphological, mineralogical and chemical traces. It is thus considered crucial to tackle the problems emerging in the search for evidence of early life on Earth and in exopaleontological research with a multidisciplinary approach. With this is mind we applied surface sensitive Time of Flight-Secondary Ion Mass Spectroscopy (ToF-SIMS) to a previously described 25 m.y. old fossil bacterial biofilm. This technique allows in situ analysis with high mass resolution as well as molecular imaging of micron sized structures. As no extraction or derivatisation of the sample is required for ToF-SIMS analysis, electron microscopical investigation of the same samples subsequent to analysis is possible, thus allowing the combination of molecular and morphological biomarkers. The analysed fossil bacterial biofilms were associated with macrofossils from volcanoclastic lacustrine sediments from the Upper Oligocene Enspel formation (Germany). Preliminary scanning electron microscopy (SEM) studies have shown that a fossil structure interpreted as a coprolite purely consisted of fossilized bacterial biofilm. For ToF-SIMS investigation small particles were taken from the fossil biofilm and mounted onto Au-coated In-foil and analysed in a Phi Evans T-2000 TRIFT system. The ToF-SIMS analysed samples were Au/Pd-sputter coated and imaged using a Philips XL40 Field Emission Gun SEM (FEG-SEM). ToF-SIMS analysis of the organic rich fossil biofilm (TOC 29%) in the 0-100 Dalton (Da) range showed significant amounts of inorganic species, confirming the results obtained previously by EDX analysis, clearly showing the bacterial fossils to be mineralised. ToF-SIMS furthermore revealed the presence of a variety of low- and high-mass organic molecules and fragments thereof. These include peaks indicative of alkenes and alkanes, aromatic organic species and the polycyclic aromatic hydrocarbon naphthalene. More tentatively, peaks indicative of alkyl pyrroles and pyridyl-CH2 were identified. Other peaks of interest include peaks indicative of C(n)H(2n)O2 and C(n)H(2n-2)O2, which according to their general formula would suggest the presence of both saturated and unsaturated fatty acids although further in situ derivatisation experiments and GC-MS (Gas Chromatography MS) need to be applied to verify this beyond doubt. Furthermore, peaks at m/z 370, 384, 398, 412, 426, 440, 454 and 468 were identified, which indicate the potential presence of bacterial hopanes, a class of biomarkers indicative of bacteria. The main diagnostic peak for this group of chemicals is the fragment at m/z 191.18. Our studies conducted on purified hopane standards have shown that in the high-mass resolution mode differentiation of this diagnostic hopane peak and polyethylene at m/z 191.05 is possible. However, the spectra discussed here were collected in the lower resolution mapping mode, therefore this differentiation was not possible. The centroids of the possible hopane peaks obtained on the fossil biofilms are well within the range associated with bacterial hopanes. There is a strong possibility therefore that hopanoids may be associated with the fossil bacterial cells. Due to the non-destructive nature of ToF-SIMS, analysed samples can be studied using SEM, thus allowing the combination of morphological and molecular biomarkers. Subsequent SEM analysis of the ToF-SIMS analysed samples confirmed that the analysed material purely consists of fossil bacterial cells. This is thus the first successful effort to demonstrate the combination of spectral and morphological biomarkers. The advantages of highly sensitive non-destructive in situ analysis techniques for biomarker detection are invaluable, particularly with respect to envisaged Mars sample return missions, as it may allow us to identify remains and traces of former microbial life in both ancient terrestrial and extraterrestrial materials. This technique may prove particularly useful in the quest for extraterrestrial life with respect to precious extraterrestrial materials, as minute quantities are sufficient to conduct analysis.

Toporski, J.↗

Elemental and charge state composition of the fast solar wind observed with SMS instruments on WIND

The elemental composition and charge state distributions of heavy ions of the solar wind provide essential information about: (1) atom-ion separation processes in the solar atmosphere leading to the 'FIP effect' (the overabundance of low First Ionization potential (FIP) elements in the solar wind compared to the photosphere); and (2) coronal temperature profiles, as well as mechanisms which heat the corona and accelerate the solar wind. This information is required for solar wind acceleration models. The SWICS instrument on Ulysses measures for all solar wind flow conditions the relative abundance of about 8 elements and 20 charge states of the solar wind. Furthermore, the Ulysses high-latitude orbit provides an unprecedented look at the solar wind from the polar coronal holes near solar minimum conditions. The MASS instrument on the WIND spacecraft is a high-mass resolution solar wind ion mass spectrometer that will provide routinely not only the abundances and charge state of all elements easily measured with SWICS, but also of N, Mg, S. The MASS sensor was fully operational at the end of 1994 and has sampled the in-ecliptic solar wind composition in both the slow and the corotating fast streams. This unique combination of SWICS on Ulysses and MASS on WIND allows us to view for the first time the solar wind from two regions of the large coronal hole. Observations with SWICS in the coronal hole wind: (1) indicate that the FIP effect is small; and (2) allow us determine the altitude of the maximum in the electron temperature profile, and indicate a maximum temperature of approximately 1.5 MK. New results from the SMS instruments on Wind will be compared with results from SWICS on Ulysses.

Gloeckler, G.↗

Carbynes in meteorites - Detection, low-temperature origin, and implications for interstellar molecules

The presence, origin and implications of carbynes in meteorites are investigated. A sample of the Allende meteorite was pyrolyzed at temperatures from 25 to 750 C and examined by solid probe time-of-flight mass spectrometry and high-resolution mass spectrometry. Fragments released upon heating at 250 to 330 C are found to be composed of macromolecules containing triply bonded carbon units and cyanoacetylenes, as well as some methyl- and phenylacetylenes. Although carbynes are well known to form from the condensation of carbon vapors above 2600 K or by shock greater than 600 kbar, which would be unlikely in Allende, it is found that carbynes rather than graphite are formed metastably by the disproportionation of CO at low temperatures when chromite is present as a catalyst. Results imply that metastable formation mechanisms may be the principal source of interstellar polycyanoacetylenes and meteoritic and terrestrial carbynes.

Hayatsu, R.↗

Laser Time-of-Flight Mass Spectrometry for Space

A miniature reflection time-of-flight mass spectrometer for in situ planetary surface analysis is described. The laser ablation mass spectrometer (LAMS) measures the regolith's elemental and isotopic composition without high-voltage source extraction or sample preparation. The compact size (< 2 x 10(exp 3) cubic cm) and low mass (approximately 2 kg) of LAMS, due to its fully coaxial design and two-stage reflectron, fall within the strict resource limitations of landed science missions to solar system bodies. A short-pulse laser focused to a spot with a diameter approximately 30-50 micrometers is used to obtain microscopic surface samples. Assisted by a microimager, LAMS can interactively select and analyze a range of compositional regions (with lateral motion) and with repeated pulses can access unweathered, subsurface materials. The mass resolution is calibrated to distinguish isotopic peaks at unit masses, and detection limits are on resolved to a few ppm. The design and calibration method of a prototype LAMS device is described, which include the development of preliminary relative sensitivity coefficients for major element bulk abundance measurements.

Brinckerhoff, W. B.↗

A satellite-borne ion mass spectrometer for the energy range 0 to 16 keV

The Ion Composition Experiment (ICE) on GEOS represents the first comprehensive attempt to measure the positive ion composition at high altitudes in the magnetosphere. Due to the heterogeneous nature of the magnetospheric plasma a novel mass spectrometer has been developed to cover the mass per charge range from H-1(+) to beyond Ba-138(+) and the energy per charge range from 0 to 16 keV/e. The ICE consists primarily of a cylindrical electrostatic analyzer followed by a curved analyzer incorporating crossed magnetic and electric fields. This combination has limited angular and energy focusing properties, but it maintains a mass resolution of about 4 over a wide range in energy and mass, sufficient for the objectives of measuring plasmas of both solar and terrestrial origin. High sensitivity and low background should allow measurements of rarer ion constituents down to flux levels of 0.01 ions/sq cm sec ster eV. A sophisticated electronics combined with powerful ground computer and telecommand systems allow for very efficient scanning of the mass-energy space.

Balsiger, H.↗