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At least 109 records · Page 6

Development of a Robust, High Current, Low Power Field Emission Electron Gun for a Spaceflight Reflectron Time-of-Flight Mass Spectrometer

Carbon materials, including carbon nanotubes (CNTs) and nitrogen-incorporated ultrananocrystalline diamond (N-UNCD), have been of considerable interest for field emission applications for over a decade. In particular, robust field emission materials are compelling for space applications due to the low power consumption and potential for miniaturization. A reflectron time-of-flight mass spectrometer (TOF-MS) under development for in situ measurements on the Moon and other Solar System bodies uses a field emitter to generate ions from gaseous samples, using electron ionization. For these unusual environments, robustness, reliability, and long life are of paramount importance, and to this end, we have explored the field emission properties and lifetime of carbon nanotubes and nitrogen-incorporated ultrananocrystalline diamond (N-UNCD) thin films, the latter developed and patented by Argonne National Laboratory. We will present recent investigations of N-UNCD as a robust field emitter, revealing that this material offers stable performance in high vacuum for up to 1000 hours with threshold voltage for emission of about 3-4 V/lJm and current densities in the range of tens of microA. Optimizing the mass resolution and sensitivity of such a mass spectrometer has also been enabled by a parallel effort to scale up a CNT emitter to an array measuring 2 mm x 40 mm. Through simulation and experiment of the new extended format emitter, we have determined that focusing the electron beam is limited due to the angular spread of the emitted electrons. This dispersion effect can be reduced through modification of the electron gun geometry, but this reduces the current reaching the ionization region. By increasing the transmission efficiency of the electron beam to the anode, we have increased the anode current by two orders of magnitude to realize a corresponding enhancement in instrument sensitivity, at a moderate cost to mass resolution. We will report recent experimental and modeling results to describe the performance of a field emission electron gun as employed in the Volatile Analysis by Pyrolysis of Regolith (VAPoR) TOF-MS prototype.

Southard, Adrian E.↗

Cerenkov x total energy telescopes for the study of the mass composition of cosmic rays

The mass resolution attainable with cosmic ray telescopes employing Cerenkov counters for velocity measurement was examined. It is shown that in most cases, the limiting mass resolution is determined by the resolution of the Cerenkov counter. The resolution achieved in the UNH telescope flown on a balloon in 1977 is studied as a function of charge and energy. This telescope determines the mass using the Cerenkov x total energy technique. It is shown that the mass resolution for heavier nuclei can be accurately predicted using the response of the Cerenkov counter to sea level mu-mesons. The actual in flight resolution for heavier nuclei, including broadening effects, may be predicted using the beta = 1 Cerenkov distributions, and independently by studying the distribution function of the differences of the two banks of photomultipliers employed on each Cerenkov counter.

Webber, W. R.↗

ESI-MS Identification of the Cationic Phosphine-Ligated Gold Clusters Au1-Au22: Insight into the Gold-Ligand Ratio and Abundance of Larger Clusters

Triphenylphosphine (PPh3)-ligated gold clusters offer promising potential applications due to their relative ease of synthesis and usefulness in forming advanced cluster architectures. While previous studies reported cationic PPh3-ligated gold clusters with core sizes of Au1 - Au4, Au6 - Au11, and Au¬13 - Au14, there has not been definitive identification by mass spectrometry of larger clusters in the Au12 - Au25¬ range. Herein, we survey a polydisperse solution of cationic PPh3-ligated gold clusters using high mass-resolution (M/?M = 60,000) electrospray ionization mass spectrometry (ESI-MS). To improve the sensitivity and mass resolution of larger clusters for unambiguous identification, we increased the number of scan averages and reduced the range of mass collection windows to 200 m/z, thereby mitigating potential mass and ion abundance bias resulting from smaller “building block” gold clusters and other solution components present in higher abundance. In addition to the previously reported clusters, we identified several new species including Au5(PPh3)5+, Au12(PPh3)9HCl2+, Au15(PPh3)9Cl2+, Au16(PPh3)10Cl22+, Au17(PPh3)113+, Au18(PPh3)102+, Au19(PPh3)10Cl2+, Au20(PPh3)12H33+, Au21(PPh3)10Cl2+, and Au22(PPh3)10Cl22+, indicating that a full range of clusters between Au1 - Au22 may be observed in a single polydisperse solution. Considering all of the observed clusters, our findings provide evidence that the “magic number” icosahedral Au13 may be the transition point in cluster growth between smaller clusters, exhibiting a 1:1 gold-to-ligand ratio, and larger clusters, wherein subsequent gold atoms are added to the core without an equal number of accompanying ligands. Our method demonstrates that reducing the range of m/z collection windows and increasing the number of scan averages can improve instrument sensitivity for cationic gold clusters and enable a more complete survey of polydisperse solutions, thereby providing new insights to guide and validate the results of other characterization methods and theoretical calculations. This work was supported by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MH acknowledges support from the DOE Science Undergraduate Laboratory Internship (SULI) program. HH acknowledges support from the DOE Office of Workforce Development for Teachers and Scientist (WDTS) under the Visiting Faculty Program (VFP). This work was performed using EMSL, a national scientific user facility sponsored by the DOE's Office of Biological and Environmental Research and located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for DOE by Battelle.

Hewitt, Michael↗

Absolute mass calibration of fission product distributions measured with the E-$v$ method

The mass calibration of fission product distributions measured with the energy–velocity (E-v) method constitutes a technical challenge. The energy loss of the fission fragments in the various dead layers of the spectrometer and other sources of pulse-height defects of the energy detectors are a significant source of systematic uncertainty in the mass calculations used to determine the measured fission product yields. Here, in this study, the absolute calibration of the fission mass distributions is accomplished by measuring prompt γ-rays in coincidence with the fission fragments. This allows for the direct calibration of the mass spectra and eliminates any dependence on potentially complicated energy corrections. The first test measurement was performed at the Los Alamos Neutron Science Center employing the SPectrometer for Ion DEtermination in fission Research (SPIDER). SPIDER is a 2E-2v spectrometer designed for measuring independent fission product yields from neutron-induced fission. In this test, the single-arm SPIDER (E-v) system and an array of 252 Cf sources were used. The single-arm system consisted of two time pick-off detectors for measuring the time-of-flight of the fission fragments and a double-sided silicon strip detector (DSSD) for measuring the kinetic energy. Characteristic γ-rays from fission fragments were detected using three high-purity germanium (HPGe) detectors. For the mass calibration, γ–mass coincidence events from twelve product isotopes were used. The measured FPYs from 252 Cf spontaneous fission were found to be in excellent agreement with the evaluated data after applying the absolute mass calibration. From the γ–mass coincidence events, the mass resolution of the system was also extracted. An average mass resolution of ~1.4 AMU (FWHM) for the light fragments and ~2.4 AMU (FWHM) for the heavy fragments were found. This was the first in-situ calibration and characterization of the SPIDER spectrometer, which paves the way for high-quality FPY measurements with this instrument.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The DESI N -body simulation project – I. Testing the robustness of simulations for the DESI dark time survey

ABSTRACT Analysis of large galaxy surveys requires confidence in the robustness of numerical simulation methods. The simulations are used to construct mock galaxy catalogues to validate data analysis pipelines and identify potential systematics. We compare three N-body simulation codes, abacus, gadget-2, and swift, to investigate the regimes in which their results agree. We run N-body simulations at three different mass resolutions, 6.25 × 108, 2.11 × 109, and 5.00 × 109 h−1 M⊙, matching phases to reduce the noise within the comparisons. We find systematic errors in the halo clustering between different codes are smaller than the Dark Energy Spectroscopic Instrument (DESI) statistical error for $s\ \gt\ 20\ h^{-1}$ Mpc in the correlation function in redshift space. Through the resolution comparison we find that simulations run with a mass resolution of 2.1 × 109 h−1 M⊙ are sufficiently converged for systematic effects in the halo clustering to be smaller than the DESI statistical error at scales larger than $20\ h^{-1}$ Mpc. These findings show that the simulations are robust for extracting cosmological information from large scales which is the key goal of the DESI survey. Comparing matter power spectra, we find the codes agree to within 1 per cent for k ≤ 10 h Mpc−1. We also run a comparison of three initial condition generation codes and find good agreement. In addition, we include a quasi-N-body code, FastPM, since we plan use it for certain DESI analyses. The impact of the halo definition and galaxy–halo relation will be presented in a follow-up study.

79 ASTRONOMY AND ASTROPHYSICS↗

Fast Airborne Aerosol Size and Chemistry Measurements with the High Resolution Aerosol Mass Spectrometer during the MILAGRO Campaign

The concentration, size, and composition of non-refractory submicron aerosol (NR-PM(sub l)) was measured over Mexico City and central Mexico with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) onboard the NSF/NCAR C-130 aircraft as part of the MILAGRO field campaign. This was the first aircraft deployment of the HR-ToF-AMS. During the campaign the instrument performed very well, and provided 12 s data. The aerosol mass from the AMS correlates strongly with other aerosol measurements on board the aircraft. Organic aerosol (OA) species dominate the NR-PM(sub l) mass. OA correlates strongly with CO and HCN indicating that pollution (mostly secondary OA, SOA) and biomass burning (BB) are the main OA sources. The OA to CO ratio indicates a typical value for aged air of around 80 microg/cubic m (STP) ppm(exp -1). This is within the range observed in outflow from the Northeastern US, which could be due to a compensating effect between higher BB but lower biogenic VOC emissions during this study. The O/C atomic ratio for OA is calculated from the HR mass spectra and shows a clear increase with photochemical age, as SOA forms rapidly and quickly overwhelms primary urban OA, consistent with Volkamer et al. (2006) and Kleinman et al. (2008). The stability of the OA/CO while O/C increases with photochemical age implies a net loss of carbon from the OA. BB OA is marked by signals at m/z 60 and 73, and also by a signal enhancement at large m/z indicative of larger molecules or more resistance to fragmentation. The main inorganic components show different spatial patterns and size distributions. Sulfate is regional in nature with clear volcanic and petrochemical/power plant sources, while the urban area is not a major regional source for this species. Nitrate is enhanced significantly in the urban area and immediate outflow, and is strongly correlated with CO indicating a strong urban source. The importance of nitrate decreases with distance from the city likely due to evaporation. BB does not appear to be a strong source of nitrate despite its high emissions of nitrogen oxides, presumably due to low ammonia emissions. NR-chloride often correlates with HCN indicating a fire source, although other sources likely contribute as well. This is the first aircraft study of the regional evolution of aerosol chemistry from a tropical megacity.

DeCarlo, P. F.↗

Functionalization of Electrodes with Tunable [EMIM] x [Cl] x +1 – Ionic Liquid Clusters for Electrochemical Separations

Functionalization of electrodes with clusters of hydrophobic molecules may improve the energy efficiency and selectivity of electrochemical separations by modulating the desolvation process occurring at the interface. Ionic liquids (IL), which have a broad range of compositions and properties, are potential candidates for controlling the transport, desolvation, and adsorption of target ions at electrochemical interfaces. We report a joint experimental and theoretical investigation of the structure, stability, and selective adsorption properties of the IL clusters 1-ethyl-3-methylimidazolium chloride [EMIM] x [Cl] x+1 - (x = 1 – 10) and demonstrate their ability to adsorb and separate ions from solution. The structure and stability of the IL clusters are determined experimentally using high-mass-resolution electrospray ionization mass spectrometry, collision-induced dissociation, and negative ion photoelectron spectroscopy. Global optimization theory and ab initio molecular dynamics simulations provide molecular-level insight into the bonding and structural fluxionality of these species. Ion soft landing is used to selectively functionalize the surface of highly oriented pyrolytic graphite (HOPG) working electrodes with [EMIM] 1 [Cl] 2 - , [EMIM] 3 [Cl] 4 - , and [EMIM] 5 [Cl] 6 - clusters. Kelvin probe microscopy provides insight into the relative stability of the clusters on HOPG and their effect on the work function of IL-functionalized electrodes. Cyclic voltammetry measurements reveal irreversible adsorption of Fe(CN) 6 4-/3- anions during redox cycling, while electrochemical impedance spectroscopy indicates a substantial decrease in the electron transfer resistance of the IL-functionalized electrodes due to adsorption of Fe(CN) 6 4-/3- . Overall, our findings demonstrate that IL clusters with different size and stoichiometry may be used to increase the efficiency of electrochemical separations, opening new horizons in selective electrode functionalization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Light Exposure Promotes Degradation of Intermediates and Growth of Phosphine-Ligated Gold Clusters

Subnanometer clusters exhibit unique properties not observed at the bulk or nanometer scale. Many applications, however, require clusters to be monodisperse in size and composition.While substantial progress has been made empirically on producing specific-sized gold clusters using different ligands, the mechanisms of cluster formation remain insufficiently understood. Using high mass-resolution electrospray ionization mass spectrometry (ESI-MS), we characterized the formation of cationic triphenylphosphine-ligated gold clusters [Aux(PPh3)y z+] in solution. Our data provides evidence that small hydrogen-containing intermediate “building blocks” (i.e., Au2(PPh3)2H+, Au4(PPh3)4H+, and Au7(PPh3)7H5 2+) are responsible for the growth of larger gold clusters (i.e., Au6(PPh3)6 2+ and Au8(PPh3)7 2+) over several hours. In addition, intermediate degradation and cluster growth are shown to be dependent on irradiation of the reacting solution with light. Specifically, the rate of growth of large clusters is demonstrated to scale with the intensity of light exposure. Complementary theoretical calculations were also performed that provide molecular-level insight into the nature of the bonding between the hydrogens and gold atoms in the intermediate Au-phosphine clusters. Collectively, our joint experimental and theoretical findings advance the understanding of the factors at play in the size-selective synthesis of ligated gold clusters in solution.

Hewitt, Michael A.↗

Structure and Stability of the Ionic Liquid Clusters [EMIM]n[BF4]n+1- (n = 1 – 9): Implications for Electrochemical Separations

Precise functionalization of electrodes with size-selected ionic liquid (IL) clusters may improve the application of ILs in electrochemical separations. Herein, we report our combined experimental and theoretical investigation of the IL clusters [EMIM]????[BF4]????+1- (n = 1 – 9) and demonstrate their selectivity and efficiency towards targeted adsorption of molecules from solution. The structures and energies of the IL clusters, predicted with global optimization, agree with and help interpret the ion abundances and stabilities measured by high mass resolution electrospray ionization mass spectrometry and collision induced dissociation experiments. The [EMIM][BF4]2- cluster, which was identified as the most stable IL cluster, was selectively soft landed onto a working electrode. Electrochemical impedance spectroscopy revealed a lower charge transfer resistance on the soft-landed electrode containing [EMIM] [BF_4 ]_2^- compared to an electrode prepared by drop casting of IL solution, which contains the full range of IL clusters. Our findings indicate that specific IL clusters may be used to increase the efficiency of electrochemical separations by lowering the overpotentials involved.

Zhang, Jun↗

A research in support of NASA's space science

Instrumentation, the interpretation of data from space-borne instruments and the development of theoretical studies of the Earth's environment are reported. New circuitry was introduced to the existing ion drift meter to enable the detection of light ion velocities that are different from the major ion species. Significant progress was made in the tailoring of magnetic mass analysis to stratospheric ions where care must be taken to preserve the original species and to obtain good mass resolution at high mass numbers. Also a rugged and durable zoom imaging spectrometer was successfully tested and important modifications are being undertaken to allow larger scanning ranges for observation of weak airglow emissions from the Earth's atmosphere. Data interpretation efforts led to the discovery of a new class of plasma irregularities on the bottomside of the F-region. Studies of all the available plasma properties from satellite measurements in the high latitude ionosphere revealed regions of field aligned currents where it is reasonable to expect thermal electrons to be the dominant current carriers.

Hanson, W. B.↗

Optimizing Simulation Parameters for Weak Lensing Analyses Involving Non-Gaussian Observables

We performed a series of numerical experiments to quantify the sensitivity of the predictions for weak lensing statistics obtained in ray-tracing dark matter (DM)-only simulations, to two hyper-parameters that influence the accuracy as well as the computational cost of the predictions: the thickness of the lens planes used to build past light cones and the mass resolution of the underlying DM simulation. The statistics considered are the power spectrum (PS) and a series of non-Gaussian observables, including the one-point probability density function, lensing peaks, and Minkowski functionals. Counterintuitively, we find that using thin lens planes (< 60 h {sup −1} Mpc on a 240 h {sup −1} Mpc simulation box) suppresses the PS over a broad range of scales beyond what would be acceptable for a survey comparable to the Large Synoptic Survey Telescope (LSST). A mass resolution of 7.2 × 10{sup 11} h {sup −1} M {sub ⊙} per DM particle (or 256{sup 3} particles in a (240 h {sup −1} Mpc){sup 3} box) is sufficient to extract information using the PS and non-Gaussian statistics from weak lensing data at angular scales down to 1′ with LSST-like levels of shape noise.

79 ASTRONOMY AND ASTROPHYSICS↗

Ion microprobe elemental analyses of impact features on interplanetary dust experiment sensor surfaces

Hypervelocity impact features on several of the electro-active dust sensors utilized in the Interplanetary Dust Experiment (IDE) were subjected to elemental analysis using an ion microprobe. The negatively biased dust sensor surfaces acted as ion traps for cations produced in the plasma plumes of impacting particles. Impactor residue surrounds most impact features to two or three feature diameters. After etching away a layer of carbonaceous/silicaceous surface contamination, low mass resolution elemental survey scans are used to tentatively identify the presence of impactor debris. High mass resolution two-dimensional elemental maps and three dimensional depth profiling of the feature and surrounding area show the distribution and relative composition of the debris. The location of these sensors on the six primary Long Duration Exposure Facility (LDEF) sides provides a unique opportunity to further define the debris environment. Researchers applied the same techniques to impact and contaminant features on a set of ultra-pure, highly polished single crystal germanium wafer witness plates that were mounted on row 12 and exposed to the environment during the entire mission.

Hunter, Jerry L.↗

Random forest models accurately classify synthetic opioids using high-dimensionality mass spectrometry datasets

Detection of novel threat agents presents several challenges, a principle one being the development of untargeted methods to screen an increasing number of threat chemicals whose exact structures are unknown. With the use of Machine Learning (ML) tools, we can guide the development of analytical methods for broad-spectrum detection of unbounded threat chemical families in complex mixtures. Toward this goal, we used nominal mass and high-resolution mass spectrometry data for hundreds of synthetic opioids and non-opioid compounds. We tested two ML techniques, logistic regression and random forest, to develop models towards a practical, implementable method for opioid detection. We found that of these tested ML methods, random forest models resulted in the highest validation accuracy (95+%) for both nominal mass and high-resolution classification of opioids versus non-opioids, with low false positive and false negative rates. The RF models were then used to successfully predict the classification of 10 compounds—five opioids and five non-opioids not part of the training and validation analysis. This application of ML is a critical step towards the development of field-deployable nominal mass spectrometers with ML-driven analyses for classification of emergent threats.

Chemistry↗

Random forest models accurately classify synthetic opioids using high-dimensionality mass spectrometry datasets

Detection of novel threat agents presents several challenges, a principle one being the development of untargeted methods to screen an increasing number of threat chemicals whose exact structures are unknown. With the use of Machine Learning (ML) tools, we can guide the development of analytical methods for broad-spectrum detection of unbounded threat chemical families in complex mixtures. Toward this goal, we used nominal mass and high-resolution mass spectrometry data for hundreds of synthetic opioids and non-opioid compounds. We tested two ML techniques, logistic regression and random forest, to develop models towards a practical, implementable method for opioid detection. We found that of these tested ML methods, random forest models resulted in the highest validation accuracy (95+%) for both nominal mass and high-resolution classification of opioids versus non-opioids, with low false positive and false negative rates. The RF models were then used to successfully predict the classification of 10 compounds—five opioids and five non-opioids not part of the training and validation analysis. This application of ML is a critical step towards the development of field-deployable nominal mass spectrometers with ML-driven analyses for classification of emergent threats.

Arasteh, Kourosh [Lawrence Livermore National Labo↗

Abundance of the Radioactive Be-10 in the Cosmic Radiation up to 2 GeVnucleon-l with the Balloon-borne Instrument ISOMAX1998

The Isotope Magnet Experiment (ISOMAX) a balloon-borne superconducting magnet spectrometer was designed to measure the isotopic composition of the light isotopes (3 less than or equal to Z less than or equal to 8) of the cosmic radiation up to 4 GeV nucleon (exp -1) with a mass resolution of better than 0.25 amu by using the velocity vs. rigidity technique. To achieve this stringent mass resolution ISOMAX was comprised of three major detector systems, a magnetic rigidity spectrometer with a precision drift chamber tracker in conjunction with a three-layer time-of-flight system and two silica-aerogel Cherenkov counters for the velocity determination. A special emphasis of the ISOMAX program was the accurate measurement of radioactive Be-10 with respect to its stable neighbor isotope Be-9, which provides important constraints on the age of cosmic rays in the Galaxy. ISOMAX had its first balloon flight on August 4-5, 1998, from Lynn Lake, Manitoba, Canada. Thirteen hours of data were recorded during this flight at a residual atmosphere of less than 5 g per square centimeter. The isotopic ratio at the top of the atmosphere for Be-10/Be-9 was measured to be 0.195 plus or minus 0.036 (statistical) plus or minus 0.039 (systematic) between 0.26 - 1.03GeV nucleon (exp -1) and 0.317 plus or minus 0.109 (statistical) plus or minus 0.042 (systematic) between 1.13 - 2.03GeV nucleon(exp -1). This is the first measurement of its kind above 1 GeV nucleon (exp -1). ISOMAX results tend to be higher than predictions from current propagation models.

Hams, T.↗

Measurement of the Abundance of Radioactive Be-10 and Other Light Isotopes in Cosmic Radiation Up to 2 GeV /Nucleon with the Balloon-Borne Instrument Isomax

The Isotope Magnet Experiment (ISOMAX), a balloon-borne superconducting magnet spectrometer, was designed to measure the isotopic composition of the light isotopes (3 les than or = Z less than or = 8) of cosmic radiation up to 4 GeV/nucleon with a mass resolution of better than 0.25 amu by using the velocity versus rigidity technique. To achieve this stringent mass resolution, ISOMAX was composed of three major detector systems: a magnetic rigidity spectrometer with a precision drift chamber tracker in conjunction with a three-layer time-of-flight system, and two silica-aerogel Cerenkov counters for velocity determination. A special emphasis of the ISOMAX program was the accurate measurement of radioactive Be-10 with respect to its stable neighbor isotope Be-9, which provides important constraints on the age of cosmic rays in the Galaxy. ISOMAX had its first balloon flight on 1998 August 4-5 from Lynn Lake, Manitoba, Canada. Thirteen hours of data were recorded during this flight at a residual atmosphere of less than 5 g/sq cm. The isotopic ratio at the top of the atmosphere for Be-10/Be-9 was measured to be 0.195 +/- 0.036 (statistical) +/- 0.039 (systematic) between 0.26 and 1.03 GeV/nucleon and 0.317 +/- 0.109(statistical) +/- 0.042(systematic) between 1.13 and 2.03 GeV/nucleon. This is the first measurement of its kind above l GeV/nucleon. ISOMAX results tend to be higher than predictions from current propagation models. In addition to the beryllium results, we report the isotopic ratios of neighboring lithium and boron in the energy range of the time-of-flight system (up to approx. 1 GeV/nucleon). The lithium and boron ratios agree well with existing data and model predictions at similar energies.

Hams, T.↗

Evolution of the Cerenkov x total-energy telescope for isotopic analysis of cosmic rays

This paper discusses the evolution of the Cerenkov x total energy technique for isotopic analysis of cosmic rays as developed by the University of New Hampshire. This technique is generally restricted to particles with Z greater than 6, and the best mass resolution is achieved over a relatively narrow energy range just above the Cerenkov threshold. State-of-the-art mass resolution is now 0.3-0.4 AMU throughout the charge range z = 8-28 and over an energy range varying from about 40 MeV/n at lower Z to about 200 MeV/n for Fe.

Webber, W. R.↗

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↗