Atmospheric sampling glow discharge ionization source

DOEpatents

McLuckey, Scott A.; Glish, Gary L.

1989-01-01

An atmospheric sampling glow discharge ionization source that can be used in combination with an analytical instrument which operates at high vacuum, such as a mass spectrometer. The atmospheric sampling glow discharge ionization source comprises a chamber with at least one pair of electrodes disposed therein, an inlet for a gaseous sample to be analyzed and an outlet communicating with an analyzer which operates at subatmospheric pressure. The ionization chamber is maintained at a pressure below atmospheric pressure, and a voltage difference is applied across the electrodes to induce a glow discharge between the electrodes, so that molecules passing through the inlet are ionized by the glow discharge and directed into the analyzer. The ionization source accepts the sample under atmospheric pressure conditions and processes it directly into the high vacuum instrument, bridging the pressure gap and drawing off unwanted atmospheric gases. The invention also includes a method for analyzing a gaseous sample using the glow discharge ionization source described above.

Asymmetric Flow Field Flow Fractionation of Aqueous C60 Nanoparticles with Size Determination by Dynamic Light Scattering and Quantification by Liquid Chromatography Atmospheric Pressure Photo-Ionization Mass Spectrometry

EPA Science Inventory

A size separation method was developed for aqueous C60 fullerene aggregates (aqu/C60) using asymmetric flow field flow fractionation (AF4) coupled to a dynamic light scattering detector in flow through mode. Surfactants, which are commonly used in AF4, were avoided as they may al...

Measurement of nonlinear refractive index and ionization rates in air using a wavefront sensor.

PubMed

Schwarz, Jens; Rambo, Patrick; Kimmel, Mark; Atherton, Briggs

2012-04-09

A wavefront sensor has been used to measure the Kerr nonlinear focal shift of a high intensity ultrashort pulse beam in a focusing beam geometry while accounting for the effects of plasma-defocusing. It is shown that plasma-defocusing plays a major role in the nonlinear focusing dynamics and that measurements of Kerr nonlinearity and ionization are coupled. Furthermore, this coupled effect leads to a novel way that measures the laser ionization rates in air under atmospheric conditions as well as Kerr nonlinearity. The measured nonlinear index n₂ compares well with values found in the literature and the measured ionization rates could be successfully benchmarked to the model developed by Perelomov, Popov, and Terentev (PPT model) [Sov. Phys. JETP 50, 1393 (1966)].

Atmospheric sampling glow discharge ionization source

DOEpatents

McLuckey, S.A.; Glish, G.L.

1989-07-18

An atmospheric sampling glow discharge ionization source that can be used in combination with an analytical instrument which operates at high vacuum, such as a mass spectrometer. The atmospheric sampling glow discharge ionization source comprises a chamber with at least one pair of electrodes disposed therein, an inlet for a gaseous sample to be analyzed and an outlet communicating with an analyzer which operates at subatmospheric pressure. The ionization chamber is maintained at a pressure below atmospheric pressure, and a voltage difference is applied across the electrodes to induce a glow discharge between the electrodes, so that molecules passing through the inlet are ionized by the glow discharge and directed into the analyzer. The ionization source accepts the sample under atmospheric pressure conditions and processes it directly into the high vacuum instrument, bridging the pressure gap and drawing off unwanted atmospheric gases. The invention also includes a method for analyzing a gaseous sample using the glow discharge ionization source described above. 3 figs.

Ionizing Electrons on the Martian Nightside: Structure and Variability

NASA Astrophysics Data System (ADS)

Lillis, Robert J.; Mitchell, David L.; Steckiewicz, Morgane; Brain, David; Xu, Shaosui; Weber, Tristan; Halekas, Jasper; Connerney, Jack; Espley, Jared; Benna, Mehdi; Elrod, Meredith; Thiemann, Edward; Eparvier, Frank

2018-05-01

The precipitation of suprathermal electrons is the dominant external source of energy deposition and ionization in the Martian nightside upper atmosphere and ionosphere. We investigate the spatial patterns and variability of ionizing electrons from 115 to 600 km altitude on the Martian nightside, using CO2 electron impact ionization frequency (EIIF) as our metric, examining more than 3 years of data collected in situ by the Mars Atmosphere and Volatile EvolutioN spacecraft. We characterize the behavior of EIIF with respect to altitude, solar zenith angle, solar wind pressure, and the geometry and strength of crustal magnetic fields. EIIF has a complex and correlated dependence on these factors, but we find that it generally increases with altitude and solar wind pressure, decreases with crustal magnetic field strength and does not depend detectably on solar zenith angle past 115°. The dependence is governed by (a) energy degradation and backscatter by collisions with atmospheric neutrals below 220 km and (b) magnetic field topology that permits or retards electron access to certain regions. This field topology is dynamic and varies with solar wind conditions, allowing greater electron access at higher altitudes where crustal fields are weaker and also for higher solar wind pressures, which result in stronger draped magnetic fields that push closed crustal magnetic field loops to lower altitudes. This multidimensional electron flux behavior can in the future be parameterized in an empirical model for use as input to global simulations of the nightside upper atmosphere, which currently do not account for this important source of energy.

Specific interaction between negative atmospheric ions and organic compounds in atmospheric pressure corona discharge ionization mass spectrometry.

PubMed

Sekimoto, Kanako; Sakai, Mami; Takayama, Mitsuo

2012-06-01

The interaction between negative atmospheric ions and various types of organic compounds were investigated using atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. Atmospheric negative ions such as O(2)(-), HCO(3)(-), COO(-)(COOH), NO(2)(-), NO(3)(-), and NO(3)(-)(HNO(3)) having different proton affinities served as the reactant ions for analyte ionization in APCDI in negative-ion mode. The individual atmospheric ions specifically ionized aliphatic and aromatic compounds with various functional groups as atmospheric ion adducts and deprotonated analytes. The formation of the atmospheric ion adducts under certain discharge conditions is most likely attributable to the affinity between the analyte and atmospheric ion and the concentration of the atmospheric ion produced under these conditions. The deprotonated analytes, in contrast, were generated from the adducts of the atmospheric ions with higher proton affinity attributable to efficient proton abstraction from the analyte by the atmospheric ion.

Feedbacks of Composition and Neutral Density Changes on the Structure of the Cusp Density Anomaly

NASA Astrophysics Data System (ADS)

Brinkman, D. G.; Walterscheid, R. L.; Clemmons, J. H.

2016-12-01

The Earth's magnetospheric cusp provides direct access of energetic particles to the thermosphere. These particles produce ionization and kinetic (particle) heating of the atmosphere. The increased ionization coupled with enhanced electric fields in the cusp produces increased Joule heating and ion drag forcing. These energy inputs cause large wind and temperature changes in the cusp region. Measurements by the CHAMP satellite (460-390- km altitude) have shown strongly enhanced density in the cusp region. The Streak mission (325-123 km), on the other hand, showed a relative depletion. The atmospheric response in the cusp can be sensitive to composition and neutral density changes. In response to heating in the cusp, air of heavier mean molecular weight is brought up from lower altitudes significantly affecting pressure gradients. This opposes the effects of temperature change due to heating and in-turn affects the density and winds produced in the cusp. Also changes in neutral density change the interaction between precipitating particles and the atmosphere and thus change heating rates and ionization in the region affected by cusp precipitation. In this study we assess the sensitivity of the wind and neutral density structure in the cusp region to changes in the mean molecular weight induced by neutral dynamics via advection, and the changes in particle heating rates and ionization which result from changes in neutral density. We use a high resolution two-dimensional time-dependent nonhydrostatic nonlinear dynamical model where inputs can be systematically altered. The resolution of the model allows us to examine the complete range of cusp widths. We compare the current simulations to observations by CHAMP and Streak. Acknowledgements: This material is based upon work supported by the National Aeronautics and Space Administration under Grant: NNX16AH46G issues through the Heliophysics Supporting Research Program. This research was also supported by The Aerospace Corporation's Technical Investment program

Comparison of the sensitivity of mass spectrometry atmospheric pressure ionization techniques in the analysis of porphyrinoids.

PubMed

Swider, Paweł; Lewtak, Jan P; Gryko, Daniel T; Danikiewicz, Witold

2013-10-01

The porphyrinoids chemistry is greatly dependent on the data obtained in mass spectrometry. For this reason, it is essential to determine the range of applicability of mass spectrometry ionization methods. In this study, the sensitivity of three different atmospheric pressure ionization techniques, electrospray ionization, atmospheric pressure chemical ionization and atmospheric pressure photoionization, was tested for several porphyrinods and their metallocomplexes. Electrospray ionization method was shown to be the best ionization technique because of its high sensitivity for derivatives of cyanocobalamin, free-base corroles and porphyrins. In the case of metallocorroles and metalloporphyrins, atmospheric pressure photoionization with dopant proved to be the most sensitive ionization method. It was also shown that for relatively acidic compounds, particularly for corroles, the negative ion mode provides better sensitivity than the positive ion mode. The results supply a lot of relevant information on the methodology of porphyrinoids analysis carried out by mass spectrometry. The information can be useful in designing future MS or liquid chromatography-MS experiments. Copyright © 2013 John Wiley & Sons, Ltd.

Ionization Efficiency in the Dayside Martian Upper Atmosphere

NASA Astrophysics Data System (ADS)

Cui, J.; Wu, X.-S.; Xu, S.-S.; Wang, X.-D.; Wellbrock, A.; Nordheim, T. A.; Cao, Y.-T.; Wang, W.-R.; Sun, W.-Q.; Wu, S.-Q.; Wei, Y.

2018-04-01

Combining the Mars Atmosphere and Volatile Evolution measurements of neutral atmospheric density, solar EUV/X-ray flux, and differential photoelectron intensity made during 240 nominal orbits, we calculate the ionization efficiency, defined as the ratio of the secondary (photoelectron impact) ionization rate to the primary (photon impact) ionization rate, in the dayside Martian upper atmosphere under a range of solar illumination conditions. Both the CO2 and O ionization efficiencies tend to be constant from 160 km up to 250 km, with respective median values of 0.19 ± 0.03 and 0.27 ± 0.04. These values are useful for fast calculation of the ionization rate in the dayside Martian upper atmosphere, without the need to construct photoelectron transport models. No substantial diurnal and solar cycle variations can be identified, except for a marginal trend of reduced ionization efficiency approaching the terminator. These observations are favorably interpreted by a simple scenario with ionization efficiencies, as a first approximation, determined by a comparison between relevant cross sections. Our analysis further reveals a connection between regions with strong crustal magnetic fields and regions with high ionization efficiencies, which are likely indicative of more efficient vertical transport of photoelectrons near magnetic anomalies.

Thin-layer chromatography and mass spectrometry coupled using proximal probe thermal desorption with electrospray or atmospheric pressure chemical ionization.

PubMed

Ovchinnikova, Olga S; Van Berkel, Gary J

2010-06-30

An atmospheric pressure proximal probe thermal desorption sampling method coupled with secondary ionization by electrospray or atmospheric pressure chemical ionization was demonstrated for the mass spectrometric analysis of a diverse set of compounds (dyestuffs, pharmaceuticals, explosives and pesticides) separated on various high-performance thin-layer chromatography plates. Line scans along or through development lanes on the plates were carried out by moving the plate relative to a stationary heated probe positioned close to or just touching the stationary phase surface. Vapors of the compounds thermally desorbed from the surface were drawn into the ionization region of a combined electrospray ionization/atmospheric pressure chemical ionization source where they merged with reagent ions and/or charged droplets from a corona discharge or an electrospray emitter and were ionized. The ionized components were then drawn through the atmospheric pressure sampling orifice into the vacuum region of a triple quadrupole mass spectrometer and detected using full scan, single ion monitoring, or selected reaction monitoring mode. Studies of variable parameters and performance metrics including the proximal probe temperature, gas flow rate into the ionization region, surface scan speed, read-out resolution, detection limits, and surface type are discussed.

A Corona Discharge Initiated Electrochemical Electrospray Ionization Technique

PubMed Central

Lloyd, John R.; Hess, Sonja

2009-01-01

We report here the development of a corona discharge (CD) initiated electrochemical (EC) electrospray ionization (ESI) technique using a standard electrospray ion source. This is a new ionization technique distinct from ESI, electrochemistry inherent to ESI, APCI, and techniques using hydroxyl radicals produced under atmospheric pressure conditions. By maximizing the observable CD at the tip of a stainless steel ESI capillary, efficient electrochemical oxidation of electrochemically active compounds is observed. For electrochemical oxidation to be observed, the ionization potential of the analyte must be lower than Fe. Ferrocene labeled compounds were chosen as the electrochemically active moiety. The electrochemical cell in the ESI source was robust and generated ions with selectivity according to the ionization potential of the analytes and up to zeptomolar sensitivity. Our results indicate that CD initiated electrochemical ionization has the potential to become a powerful technique to increase the dynamic range, sensitivity and selectivity of ESI experiments. Synopsis Using a standard ESI source a corona discharge initiated electrochemical ionization technique was established resulting from the electrochemistry occurring at the CD electrode surface. PMID:19747843

The Extreme-ultraviolet Emission from Sun-grazing Comets

NASA Technical Reports Server (NTRS)

Bryans, Paul; Pesnell, William D.

2012-01-01

The Atmospheric Imaging Assembly (AIA) on the Solar Dynamics Observatory has observed two Sun-grazing comets as they passed through the solar atmosphere. Both passages resulted in a measurable enhancement of extreme-ultraviolet (EUV) radiance in several of the AIA bandpasses.We explain this EUV emission by considering the evolution of the cometary atmosphere as it interacts with the ambient solar atmosphere. Molecules in the comet rapidly sublimate as it approaches the Sun. They are then photodissociated by the solar radiation field to create atomic species. Subsequent ionization of these atoms produces a higher abundance of ions than normally present in the corona and results in EUV emission in the wavelength ranges of the AIA telescope passbands.

The Near-Earth Plasma Environment

NASA Technical Reports Server (NTRS)

Pfaff, Robert F., Jr.

2012-01-01

An overview of the plasma environment near the earth is provided. We describe how the near-earth plasma is formed, including photo-ionization from solar photons and impact ionization at high latitudes from energetic particles. We review the fundamental characteristics of the earth's plasma environment, with emphasis on the ionosphere and its interactions with the extended neutral atmosphere. Important processes that control ionospheric physics at low, middle, and high latitudes are discussed. The general dynamics and morphology of the ionized gas at mid- and low-latitudes are described including electrodynamic contributions from wind-driven dynamos, tides, and planetary-scale waves. The unique properties of the near-earth plasma and its associated currents at high latitudes are shown to depend on precipitating auroral charged particles and strong electric fields which map earthward from the magnetosphere. The upper atmosphere is shown to have profound effects on the transfer of energy and momentum between the high-latitude plasma and the neutral constituents. The article concludes with a discussion of how the near-earth plasma responds to magnetic storms associated with solar disturbances.

Computational studies of atmospherically-relevant chemical reactions in water clusters and on liquid water and ice surfaces.

PubMed

Gerber, R Benny; Varner, Mychel E; Hammerich, Audrey D; Riikonen, Sampsa; Murdachaew, Garold; Shemesh, Dorit; Finlayson-Pitts, Barbara J

2015-02-17

CONSPECTUS: Reactions on water and ice surfaces and in other aqueous media are ubiquitous in the atmosphere, but the microscopic mechanisms of most of these processes are as yet unknown. This Account examines recent progress in atomistic simulations of such reactions and the insights provided into mechanisms and interpretation of experiments. Illustrative examples are discussed. The main computational approaches employed are classical trajectory simulations using interaction potentials derived from quantum chemical methods. This comprises both ab initio molecular dynamics (AIMD) and semiempirical molecular dynamics (SEMD), the latter referring to semiempirical quantum chemical methods. Presented examples are as follows: (i) Reaction of the (NO(+))(NO3(-)) ion pair with a water cluster to produce the atmospherically important HONO and HNO3. The simulations show that a cluster with four water molecules describes the reaction. This provides a hydrogen-bonding network supporting the transition state. The reaction is triggered by thermal structural fluctuations, and ultrafast changes in atomic partial charges play a key role. This is an example where a reaction in a small cluster can provide a model for a corresponding bulk process. The results support the proposed mechanism for production of HONO by hydrolysis of NO2 (N2O4). (ii) The reactions of gaseous HCl with N2O4 and N2O5 on liquid water surfaces. Ionization of HCl at the water/air interface is followed by nucleophilic attack of Cl(-) on N2O4 or N2O5. Both reactions proceed by an SN2 mechanism. The products are ClNO and ClNO2, precursors of atmospheric atomic chlorine. Because this mechanism cannot result from a cluster too small for HCl ionization, an extended water film model was simulated. The results explain ClNO formation experiments. Predicted ClNO2 formation is less efficient. (iii) Ionization of acids at ice surfaces. No ionization is found on ideal crystalline surfaces, but the process is efficient on isolated defects where it involves formation of H3O(+)-acid anion contact ion pairs. This behavior is found in simulations of a model of the ice quasi-liquid layer corresponding to large defect concentrations in crystalline ice. The results are in accord with experiments. (iv) Ionization of acids on wet quartz. A monolayer of water on hydroxylated silica is ordered even at room temperature, but the surface lattice constant differs significantly from that of crystalline ice. The ionization processes of HCl and H2SO4 are of high yield and occur in a few picoseconds. The results are in accord with experimental spectroscopy. (v) Photochemical reactions on water and ice. These simulations require excited state quantum chemical methods. The electronic absorption spectrum of methyl hydroperoxide adsorbed on a large ice cluster is strongly blue-shifted relative to the isolated molecule. The measured and calculated adsorption band low-frequency tails are in agreement. A simple model of photodynamics assumes prompt electronic relaxation of the excited peroxide due to the ice surface. SEMD simulations support this, with the important finding that the photochemistry takes place mainly on the ground state. In conclusion, dynamics simulations using quantum chemical potentials are a useful tool in atmospheric chemistry of water media, capable of comparison with experiment.

Energetic electron precipitation and auroral morphology at the substorm recovery phase

NASA Astrophysics Data System (ADS)

Oyama, S. I.; Kero, A.; Rodger, C. J.; Clilverd, M. A.; Yoshizumi, M.; Partamies, N.; Turunen, E. S.; Tero, R.; Verronen, P. T.; Saito, S.

2017-12-01

It is well known that auroral patterns at the substorm recovery phase are characterized by diffuse or patch structures with intensity pulsation. According to satellite measurements and simulation studies, the precipitating electrons associated with these aurorae can reach or exceed energies of a few hundred keV through resonant wave-particle interactions in the magnetosphere. However, because of difficulty of simultaneous measurements, the dependency of energetic electron precipitation (EEP) on auroral morphological changes in the mesoscale has not been investigated to date. In order to study this dependency, we have analyzed data from the European Incoherent Scatter (EISCAT) radar, the Kilpisjärvi Atmospheric Imaging Receiver Array (KAIRA) riometer, collocated cameras, ground-based magnetometers, the Van Allen Probe satellites, Polar Operational Environmental Satellites (POES), and the Antarctic-Arctic Radiation-belt (Dynamic) Deposition-VLF Atmospheric Research Konsortium (AARDDVARK). Here we undertake a detailed examination of two case studies. The selected two events suggest that the highest energy of EEP on those days occurred with auroral patch formation from post-midnight to dawn, coinciding with the substorm onset at local midnight. Measurements of the EISCAT radar showed ionization as low as 65 km altitude, corresponding to EEP with energies of about 500 keV. Enhancements of the deep ionospheric ionization induced by the EEP modify the chemical-reaction balance involving atmospheric minor species such as NOx and HOx. These species may cause reduction in the ozone density at the ionization altitude or the lower region where these species are transported by the vertical convection in the dynamics. Since the EEP is a typical phenomenon at the substorm recovery phase, the ozone density depletion may be a frequent signature although our understanding has not yet reached the maturity of the mechanism behind these evidences. This presentation will discuss the processes related to the EEP and its effects on the atmosphere through changes in the minor components.

Highly informative multiclass profiling of lipids by ultra-high performance liquid chromatography - Low resolution (quadrupole) mass spectrometry by using electrospray ionization and atmospheric pressure chemical ionization interfaces.

PubMed

Beccaria, Marco; Inferrera, Veronica; Rigano, Francesca; Gorynski, Krzysztof; Purcaro, Giorgia; Pawliszyn, Janusz; Dugo, Paola; Mondello, Luigi

2017-08-04

A simple, fast, and versatile method, using an ultra-high performance liquid chromatography system coupled with a low resolution (single quadrupole) mass spectrometer was optimized to perform multiclass lipid profiling of human plasma. Particular attention was made to develop a method suitable for both electrospray ionization and atmospheric pressure chemical ionization interfaces (sequentially in positive- and negative-ion mode), without any modification of the chromatographic conditions (mobile phase, flow-rate, gradient, etc.). Emphasis was given to the extrapolation of the structural information based on the fragmentation pattern obtained using atmospheric pressure chemical ionization interface, under each different ionization condition, highlighting the complementary information obtained using the electrospray ionization interface, of support for related molecule ions identification. Furthermore, mass spectra of phosphatidylserine and phosphatidylinositol obtained using the atmospheric pressure chemical ionization interface are reported and discussed for the first time. Copyright © 2017 Elsevier B.V. All rights reserved.

Compact cosmic ray detector for unattended atmospheric ionization monitoring

NASA Astrophysics Data System (ADS)

Aplin, K. L.; Harrison, R. G.

2010-12-01

Two vertical cosmic ray telescopes for atmospheric cosmic ray ionization event detection are compared. Counter A, designed for low power remote use, was deployed in the Welsh mountains; its event rate increased with altitude as expected from atmospheric cosmic ray absorption. Independently, Counter B's event rate was found to vary with incoming particle acceptance angle. Simultaneous co-located comparison of both telescopes exposed to atmospheric ionization showed a linear relationship between their event rates.

Solar atmospheric dynamics. II - Nonlinear models of the photospheric and chromospheric oscillations

NASA Technical Reports Server (NTRS)

Leibacher, J.; Gouttebroze, P.; Stein, R. F.

1982-01-01

The one-dimensional, nonlinear dynamics of the solar atmosphere is investigated, and models of the observed photospheric (300 s) and chromospheric (200 s) oscillations are described. These are resonances of acoustic wave cavities formed by the variation of the temperature and ionization between the subphotospheric, hydrogen convection zone and the chromosphere-corona transition region. The dependence of the oscillations upon the excitation and boundary conditions leads to the conclusion that for the observed amplitudes, the modes are independently excited and, as trapped modes, transport little if any mechanical flux. In the upper photosphere and lower chromosphere, where the two modes have comparable energy density, interference between them leads to apparent vertical phase delays which might be interpreted as evidence of an energy flux.

Interactive Ion-Neutral Dynamics in the Low Latitude Evening Ionosphere

NASA Astrophysics Data System (ADS)

Evonosky, W. R.; Richmond, A. D.; Fang, T. W.; Maute, A. I.

2015-12-01

Neutral winds in the ionosphere drive global electrodynamic phenomena which alter theupper-atmosphere so significantly that they can affect the orbit of satellites andground-to-spacecraft communications. Understanding these winds and what drives them is centralto prediction and risk management associated with such a dynamic upper atmosphere. This studyexamined the relationship between accelerations acting on neutral winds in the ionosphere and theformation of a vertical shear of those winds in low latitudes (between ±30 magnetic) and earlyevening local times (16-22 LT). Accelerations were calculated using variables output by thethermosphere ionosphere electrodynamics general circulation model (TIEGCM) under differentsolar activity and night-time ionization conditions and visualized both spatially and temporally. Ingeneral, with acceleration values averaged along magnetic latitudes between ±30 degrees(inclusive) and only considering medium solar activity conditions, we found that the ionosphereexhibits distinct layering defined by the dominant accelerations in each layer. We also found hintsthat during different night-time ionization levels, ion drag acceleration tends to remain constantwhile ion and neutral velocities change to conserve the difference between them. When consideringspecific latitudes and solar conditions, previously unreported structures appear which involveinteractions between the ion drag and viscous forces.

Particle precipitation: How the spectrum fit impacts atmospheric chemistry

NASA Astrophysics Data System (ADS)

Wissing, J. M.; Nieder, H.; Yakovchouk, O. S.; Sinnhuber, M.

2016-11-01

Particle precipitation causes atmospheric ionization. Modeled ionization rates are widely used in atmospheric chemistry/climate simulations of the upper atmosphere. As ionization rates are based on particle measurements some assumptions concerning the energy spectrum are required. While detectors measure particles binned into certain energy ranges only, the calculation of a ionization profile needs a fit for the whole energy spectrum. Therefore the following assumptions are needed: (a) fit function (e.g. power-law or Maxwellian), (b) energy range, (c) amount of segments in the spectral fit, (d) fixed or variable positions of intersections between these segments. The aim of this paper is to quantify the impact of different assumptions on ionization rates as well as their consequences for atmospheric chemistry modeling. As the assumptions about the particle spectrum are independent from the ionization model itself the results of this paper are not restricted to a single ionization model, even though the Atmospheric Ionization Module OSnabrück (AIMOS, Wissing and Kallenrode, 2009) is used here. We include protons only as this allows us to trace changes in the chemistry model directly back to the different assumptions without the need to interpret superposed ionization profiles. However, since every particle species requires a particle spectrum fit with the mentioned assumptions the results are generally applicable to all precipitating particles. The reader may argue that the selection of assumptions of the particle fit is of minor interest, but we would like to emphasize on this topic as it is a major, if not the main, source of discrepancies between different ionization models (and reality). Depending on the assumptions single ionization profiles may vary by a factor of 5, long-term calculations may show systematic over- or underestimation in specific altitudes and even for ideal setups the definition of the energy-range involves an intrinsic 25% uncertainty for the ionization rates. The effects on atmospheric chemistry (HOx, NOx and Ozone) have been calculated by 3dCTM, showing that the spectrum fit is responsible for a 8% variation in Ozone between setups, and even up to 50% for extreme setups.

Analysis of ionization wave dynamics in low-temperature plasma jets from fluid modeling supported by experimental investigations

NASA Astrophysics Data System (ADS)

Yousfi, M.; Eichwald, O.; Merbahi, N.; Jomaa, N.

2012-08-01

This work is devoted to fluid modeling based on experimental investigations of a classical setup of a low-temperature plasma jet. The latter is generated at atmospheric pressure using a quartz tube of small diameter crossed by helium gas flow and surrounded by an electrode system powered by a mono-polar high-voltage pulse. The streamer-like behavior of the fast plasma bullets or ionization waves launched in ambient air for every high-voltage pulse, already emphasized in the literature from experimental or analytical considerations or recent preliminary fluid models, is confirmed by a numerical one-moment fluid model for the simulation of the ionization wave dynamics. The dominant interactions between electron and the main ions present in He-air mixtures with their associated basic data are taken into account. The gradual dilution of helium in air outside the tube along the axis is also considered using a gas hydrodynamics model based on the Navier-Stokes equation assuming a laminar flow. Due to the low magnitude of the reduced electric field E/N (not exceeding 15 Td), it is first shown that consideration of the stepwise ionization of helium metastables is required to reach the critical size of the electron avalanches in order to initiate the formation of ionization waves. It is also shown that a gas pre-ionization ahead of the wave front of about 109 cm-3 (coming from Penning ionization without considering the gas photo-ionization) is required for the propagation. Furthermore, the second ionization wave experimentally observed during the falling time of the voltage pulse, between the powered electrode and the tube exit, is correlated with the electric field increase inside the ionized channel in the whole region between the electrode and the tube exit. The propagation velocity and the distance traveled by the front of the ionization wave outside the tube in the downstream side are consistent with the present experimental measurements. In comparison with the streamer dynamics in a classical corona discharge, it is shown that under the same gas composition the plasma jet ionization waves propagate with a lower velocity (about 5 times), and have a higher diameter (at least 10 times) and a lower plasma density (at least 100 times).

Analysis of conductive target influence in plasma jet experiments through helium metastable and electric field measurements

NASA Astrophysics Data System (ADS)

Darny, T.; Pouvesle, J.-M.; Puech, V.; Douat, C.; Dozias, S.; Robert, Eric

2017-04-01

The use of cold atmospheric pressure plasma jets for in vivo treatments implies most of the time plasma interaction with conductive targets. The effect of conductive target contact on the discharge behavior is studied here for a grounded metallic target and compared to the free jet configuration. In this work, realized with a plasma gun, we measured helium metastable HeM (23S1) concentration (by laser absorption spectroscopy) and electric field (EF) longitudinal and radial components (by electro-optic probe). Both diagnostics were temporally and spatially resolved. Mechanisms after ionization front impact on the target surface have been identified. The remnant conductive ionized channel behind the ionization front electrically transiently connects the inner high voltage electrode to the target. Due to impedance mismatching between the ionized channel and the target, a secondary ionization front is initiated and rapidly propagates from the target surface to the inner electrode through this ionized channel. This leads to a greatly enhanced HeM production inside the plasma plume and the capillary. Forward and reverse dynamics occur with further multi reflections of more or less damped ionization fronts between the inner electrode and the target as long as the ionized channel is persisting. This phenomenon is very sensitive to parameters such as target distance and ionized channel conductivity affecting electrical coupling between these two and evidenced using positive or negative voltage polarity and nitrogen admixture. In typical operating conditions for the plasma gun used in this work, it has been found that after the secondary ionization front propagation, when the ionized channel is conductive enough, a glow like discharge occurs with strong conduction current. HeM production and all species excitation, especially reactive ones, are then driven by high voltage pulse evolution. The control of forward and reverse dynamics, impacting on the production of the glow like discharge, will be useful for biomedical applications on living tissues.

Dielectric barrier discharge ionization for liquid chromatography/mass spectrometry.

PubMed

Hayen, Heiko; Michels, Antje; Franzke, Joachim

2009-12-15

An atmospheric pressure microplasma ionization source based on a dielectric barrier discharge with a helium plasma cone outside the electrode region has been developed for liquid chromatography/mass spectrometry (LC/MS). For this purpose, the plasma was realized in a commercial atmospheric pressure ionization source. Dielectric barrier discharge ionization (DBDI) was compared to conventional electrospray ionization (ESI), atmospheric pressure chemical ionization (APCI), and atmospheric pressure photoionization (APPI) in the positive ionization mode. Therefore, a heterogeneous compound library was investigated that covered polar compounds such as amino acids, water-soluble vitamins, and nonpolar compounds like polycyclic aromatic hydrocarbons and functionalized hydrocarbons. It turned out that DBDI can be regarded as a soft ionization technique characterized by only minor fragmentation similar to APCI. Mainly protonated molecules were detected. Additionally, molecular ions were observed for polycyclic aromatic hydrocarbons and derivatives thereof. During DBDI, adduct formation with acetonitrile occurred. For aromatic compounds, addition of one to four oxygen atoms and to a smaller extend one nitrogen and oxygen was observed which delivered insight into the complexity of the ionization processes. In general, compounds covering a wider range of polarities can be ionized by DBDI than by ESI. Furthermore, limits of detection compared to APCI are in most cases equal or even better.

Ionization of EPA Contaminants in Direct and Dopant-Assisted Atmospheric Pressure Photoionization and Atmospheric Pressure Laser Ionization

NASA Astrophysics Data System (ADS)

Kauppila, Tiina J.; Kersten, Hendrik; Benter, Thorsten

2015-06-01

Seventy-seven EPA priority environmental pollutants were analyzed using gas chromatography-mass spectrometry (GC-MS) equipped with an optimized atmospheric pressure photoionization (APPI) and an atmospheric pressure laser ionization (APLI) interface with and without dopants. The analyzed compounds included e.g., polycyclic aromatic hydrocarbons (PAHs), nitro compounds, halogenated compounds, aromatic compounds with phenolic, acidic, alcohol, and amino groups, phthalate and adipatic esters, and aliphatic ethers. Toluene, anisole, chlorobenzene, and acetone were tested as dopants. The widest range of analytes was ionized using direct APPI (66/77 compounds). The introduction of dopants decreased the amount of compounds ionized in APPI (e.g., 54/77 with toluene), but in many cases the ionization efficiency increased. While in direct APPI the formation of molecular ions via photoionization was the main ionization reaction, dopant-assisted (DA) APPI promoted ionization reactions, such as charge exchange and proton transfer. Direct APLI ionized a much smaller amount of compounds than APPI (41/77 compounds), showing selectivity towards compounds with low ionization energies (IEs) and long-lived resonantly excited intermediate states. DA-APLI, however, was able to ionize a higher amount of compounds (e.g. 51/77 with toluene), as the ionization took place entirely through dopant-assisted ion/molecule reactions similar to those in DA-APPI. Best ionization efficiency in APPI and APLI (both direct and DA) was obtained for PAHs and aromatics with O- and N-functionalities, whereas nitro compounds and aliphatic ethers were the most difficult to ionize. Halogenated aromatics and esters were (mainly) ionized in APPI, but not in APLI.

Atmospheric changes caused by galactic cosmic rays over the period 1960-2010

NASA Astrophysics Data System (ADS)

Jackman, Charles H.; Marsh, Daniel R.; Kinnison, Douglas E.; Mertens, Christopher J.; Fleming, Eric L.

2016-05-01

The Specified Dynamics version of the Whole Atmosphere Community Climate Model (SD-WACCM) and the Goddard Space Flight Center two-dimensional (GSFC 2-D) models are used to investigate the effect of galactic cosmic rays (GCRs) on the atmosphere over the 1960-2010 time period. The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) computation of the GCR-caused ionization rates are used in these simulations. GCR-caused maximum NOx increases of 4-15 % are computed in the Southern polar troposphere with associated ozone increases of 1-2 %. NOx increases of ˜ 1-6 % are calculated for the lower stratosphere with associated ozone decreases of 0.2-1 %. The primary impact of GCRs on ozone was due to their production of NOx. The impact of GCRs varies with the atmospheric chlorine loading, sulfate aerosol loading, and solar cycle variation. Because of the interference between the NOx and ClOx ozone loss cycles (e.g., the ClO + NO2+ M → ClONO2+ M reaction) and the change in the importance of ClOx in the ozone budget, GCRs cause larger atmospheric impacts with less chlorine loading. GCRs also cause larger atmospheric impacts with less sulfate aerosol loading and for years closer to solar minimum. GCR-caused decreases of annual average global total ozone (AAGTO) were computed to be 0.2 % or less with GCR-caused column ozone increases between 1000 and 100 hPa of 0.08 % or less and GCR-caused column ozone decreases between 100 and 1 hPa of 0.23 % or less. Although these computed ozone impacts are small, GCRs provide a natural influence on ozone and need to be quantified over long time periods. This result serves as a lower limit because of the use of the ionization model NAIRAS/HZETRN which underestimates the ion production by neglecting electromagnetic and muon branches of the cosmic ray induced cascade. This will be corrected in future works.

Discharge dynamics of pin-to-plate dielectric barrier discharge at atmospheric pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sun Liqun; Huang, Xiaojiang; Member of Magnetic Confinement Fusion Research Center, Ministry of Education of the People's Republic of China, Shanghai 201620

2010-11-15

The discharge dynamics of pin-to-plate dielectric barrier discharge was studied in atmospheric helium at 20 kHz. The discharge was predominately ignited in positive half cycle of applied voltage with sinusoidal waveform. The temporal evolution of the discharge was investigated vertically along the discharge gap and radically on the dielectric surface by time resolved imaging. It is found that a discharge column with a diameter of 2 mm was ignited above the pin electrode and expanded toward a plate electrode. On the dielectric surface with space charge accumulation, plasma disk in terms of plasma ring was formed with radius up tomore » 25 mm. The expansion velocity of plasma ring can reach a hypersonic speed of 3.0 km/s. The ionization wave due to electron diffusion is considered to be the mechanism for plasma ring formation and dynamics.« less

Discharge dynamics of pin-to-plate dielectric barrier discharge at atmospheric pressure

NASA Astrophysics Data System (ADS)

Sun, Liqun; Huang, Xiaojiang; Zhang, Jie; Zhang, Jing; Shi, J. J.

2010-11-01

The discharge dynamics of pin-to-plate dielectric barrier discharge was studied in atmospheric helium at 20 kHz. The discharge was predominately ignited in positive half cycle of applied voltage with sinusoidal waveform. The temporal evolution of the discharge was investigated vertically along the discharge gap and radically on the dielectric surface by time resolved imaging. It is found that a discharge column with a diameter of 2 mm was ignited above the pin electrode and expanded toward a plate electrode. On the dielectric surface with space charge accumulation, plasma disk in terms of plasma ring was formed with radius up to 25 mm. The expansion velocity of plasma ring can reach a hypersonic speed of 3.0 km/s. The ionization wave due to electron diffusion is considered to be the mechanism for plasma ring formation and dynamics.

Experimental investigation on large-area dielectric barrier discharge in atmospheric nitrogen and air assisted by the ultraviolet lamp.

PubMed

Zhang, Yan; Gu, Biao; Wang, Wenchun; Wang, Dezhen; Peng, Xuwen

2009-04-01

In this paper, ultraviolet radiation produced by the ultraviolet lamp is employed to supply pre-ionization for the dielectric barrier discharge in N(2) or air at atmospheric pressure. The effect of the ultraviolet pre-ionization on improving the uniformity of the dielectric barrier discharge is investigated experimentally. The atmospheric pressure glow discharge of the large area (270 mm x 120 mm) is obtained successfully via the ultraviolet pre-ionization in atmospheric DBD in N(2) when the gas gap decrease to 3mm. Based on the emission spectra, the mechanism which ultraviolet pre-ionization improves the uniformity of the dielectric barrier discharge is discussed.

Dynamic modification of optical nonlinearities related to femtosecond laser filamentation in gases

NASA Astrophysics Data System (ADS)

Romanov (1, 3), Dmitri; Tarazkar (2, 3), Maryam; Levis (2, 3), Robert

2017-04-01

During and immediately after the passing of a filamenting laser pulse through a gas-phase medium, the nonlinear optical characteristics of the emerging filament-wake channel undergo substantial transient modification, which stems from ionization and electronic excitation of constituent atoms/molecules. We calculate the related hyperpolarizability coefficients of individual ions, and we develop a theoretical model of filament channel evolution applicable to atmospheric-pressure and high-pressure gases. The evolution is mediated by energetic free-electron gas that results from the strong-field ionization and gains considerable energy via inverse Bremsstrahlung process. The ensuing impact ionization and excitation of the residual neutral atoms/molecules proceeds inhomogeneously both inside the channel and on its surface, being strongly influenced by the thermal conduction of the electron gas. The model shows critical importance of channel-surface effects, especially as regards the effective electron temperature. The calculated spatial-temporal evolution patterns ultimately determine the transient modifications of linear and nonlinear optical properties of filament wake channels. Medium-specific estimates are made for atmospheric- and high-pressure argon, as well as for molecular nitrogen gas. Support of Defense Threat Reduction Agency (Grant No. HDTRA1-12-1-0014) is gratefully acknowledged.

Modeling Atmospheric Aerosols in WRF/Chem

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yang; Hu, X.-M.; Howell, G.

2005-06-01

In this study, three aerosol modules are tested and compared. The first module is the Modal Aerosol Dynamics Model for Europe (MADE) with the secondary organic aerosol model (SORGAM) (referred to as MADE/SORGAM). The second module is the Model for Simulating Aerosol Interactions and Chemistry (MOSAIC). The third module is the Model of Aerosol Dynamics, Reaction, Ionization and Dissolution (MADRID). The three modules differ in terms of size representation used, chemical species treated, assumptions and numerical algorithms used. Table 1 compares the major processes among the three aerosol modules.

Atmospheric pressure ionization-tandem mass spectrometry of the phenicol drug family.

PubMed

Alechaga, Élida; Moyano, Encarnación; Galceran, M Teresa

2013-11-01

In this work, the mass spectrometry behaviour of the veterinary drug family of phenicols, including chloramphenicol (CAP) and its related compounds thiamphenicol (TAP), florfenicol (FF) and FF amine (FFA), was studied. Several atmospheric pressure ionization sources, electrospray (ESI), atmospheric pressure chemical ionization and atmospheric pressure photoionization were compared. In all atmospheric pressure ionization sources, CAP, TAP and FF were ionized in both positive and negative modes; while for the metabolite FFA, only positive ionization was possible. In general, in positive mode, [M + H](+) dominated the mass spectrum for FFA, while the other compounds, CAP, TAP and FF, with lower proton affinity showed intense adducts with species present in the mobile phase. In negative mode, ESI and atmospheric pressure photoionization showed the deprotonated molecule [M-H](-), while atmospheric pressure chemical ionization provided the radical molecular ion by electron capture. All these ions were characterized by tandem mass spectrometry using the combined information obtained by multistage mass spectrometry and high-resolution mass spectrometry in a quadrupole-Orbitrap instrument. In general, the fragmentation occurred via cyclization and losses or fragmentation of the N-(alkyl)acetamide group, and common fragmentation pathways were established for this family of compounds. A new chemical structure for the product ion at m/z 257 for CAP, on the basis of the MS(3) and MS(4) spectra is proposed. Thermally assisted ESI and selected reaction monitoring are proposed for the determination of these compounds by ultra high-performance liquid chromatography coupled to tandem mass spectrometry, achieving instrumental detection limits down to 0.1 pg. Copyright © 2013 John Wiley & Sons, Ltd.

Simultaneous Optical and Meteor Head Echo Measurements Using the Middle Atmosphere Alomar Radar System (MAARSY)

NASA Technical Reports Server (NTRS)

Cooke, W. J.; Brown, P. G.; Stober, G.; Schult, C.; Krzeminski, Z.; Chau, J. L.

2017-01-01

We describe a two year campaign of simultaneous automated meteor optical and head echo radar measurements conducted with the Middle Atmosphere Alomar Radar System (MAARSY). This campaign was established with the following goals: Compare trajectories as measured by MAARSY and the two optical stations for a range of meteoroid masses. Compare photometric and dynamic mass measured optically with radar-derived masses (inter-calibration of mass scales). Use the best observed simultaneous events to fuse all metric, photometric and ionization estimates together and apply different ablation models to self-consistently model these highest quality events.

Improving N-Glycan Coverage using HPLC-MS with Electrospray Ionization at Subambient Pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marginean, Ioan; Kronewitter, Scott R.; Moore, Ronald J.

Human serum glycan profiling with mass spectrometry (MS) has been employed to study several disease conditions and is demonstrating promise for e.g. clinical biomarker discovery. However, the poor glycan ionization efficiency and the large dynamic range of glycan concentrations in human sera hinder comprehensive profiling. In particular, large glycans are problematic because they are present at low concentrations and prone to fragmentation. Here we show that the sub-ambient pressure ionization with nanoelectrospray (SPIN)-MS can expand the serum glycome profile when compared with the conventional atmospheric pressure electrospray ionization (ESI)-MS with a heated capillary inlet. Notably, the ions generated by themore » SPIN interface were observed at higher charge states for 50% of the annotated glycans. Out of a total of 130 detected glycans, 34 were only detected with the SPIN-MS, resulting in improved coverage of glycan families as well as of glycans with larger numbers of labile monosaccharides.« less

Simultaneous determination of organophosphorus pesticides in fruits and vegetables using atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry.

PubMed

Cheng, Zhipeng; Dong, Fengshou; Xu, Jun; Liu, Xingang; Wu, Xiaohu; Chen, Zenglong; Pan, Xinglu; Gan, Jay; Zheng, Yongquan

2017-09-15

This paper describes the application of atmospheric pressure gas chromatography quadrupole-time-of-flight mass spectrometry for the simultaneous determination of organophosphorus pesticides in apple, pear, tomato, cucumber and cabbage. Soft ionization with atmospheric pressure ionization source was compared with traditional electron impact ionization (EI). The sensitivity of GC coupled to atmospheric pressure ionization (APGC) for all the analytes was enhanced by 1.0-8.2 times. The ionization modes with atmospheric pressure ionization source was studied by comparing the charge-transfer and proton-transfer conditions. The optimized QuEChERs method was used to pretreat the samples. The calibration curves were found linear from 10 to 1000μg/L, obtaining correlation coefficients higher than 0.9845. Satisfactory mean recovery values, in the range of 70.0-115.9%, and satisfactory precision, with all RSD r <19.7% and all RSD R values <19.5% at the three fortified concentration levels for all the fifteen OPPs. The results demonstrate the potential of APGC-QTOF-MS for routine quantitative analysis of organophosphorus pesticide in fruits and vegetables. Copyright © 2017 Elsevier Ltd. All rights reserved.

Analysis of model Titan atmospheric components using ion mobility spectrometry

NASA Technical Reports Server (NTRS)

Kojiro, D. R.; Cohen, M. J.; Wernlund, R. F.; Stimac, R. M.; Humphry, D. E.; Takeuchi, N.

1991-01-01

The Gas Chromatograph-Ion Mobility Spectrometer (GC-IMS) was proposed as an analytical technique for the analysis of Titan's atmosphere during the Cassini Mission. The IMS is an atmospheric pressure, chemical detector that produces an identifying spectrum of each chemical species measured. When the IMS is combined with a GC as a GC-IMS, the GC is used to separate the sample into its individual components, or perhaps small groups of components. The IMS is then used to detect, quantify, and identify each sample component. Conventional IMS detection and identification of sample components depends upon a source of energetic radiation, such as beta radiation, which ionizes the atmospheric pressure host gas. This primary ionization initiates a sequence of ion-molecule reactions leading to the formation of sufficiently energetic positive or negative ions, which in turn ionize most constituents in the sample. In conventional IMS, this reaction sequence is dominated by the water cluster ion. However, many of the light hydrocarbons expected in Titan's atmosphere cannot be analyzed by IMS using this mechanism at the concentrations expected. Research at NASA Ames and PCP Inc., has demonstrated IMS analysis of expected Titan atmospheric components, including saturated aliphatic hydrocarbons, using two alternate sample ionizations mechanisms. The sensitivity of the IMS to hydrocarbons such as propane and butane was increased by several orders of magnitude. Both ultra dry (waterless) IMS sample ionization and metastable ionization were successfully used to analyze a model Titan atmospheric gas mixture.

APPI-MS: Effects of mobile phases and VUV lamps on the detection of PAH compounds

PubMed Central

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A.

2009-01-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of non-polar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e., ≤100 μL/min), while at a higher flow, photon absorption and ion-molecule reactions become significant. Under certain circumstances, APPI signal and S/N have been observed to excel at higher flow, which may be due to a non-photoionzation mechanism. To better understand APPI at higher flow rates, we have selected three lamps (Xe, Kr and Ar) and four mobile phases typical for reverse-phase, high-pressure liquid chromatography: acetonitrile, methanol, (1:1) acetonitrile:water and (1:1) methanol:water. As test compounds, three polyaromatic hydrocarbons are studied: benzo[a]pyrene, indeno[1,2,3-c,d]pyrene and benz[a]anthracene. We find that solvent photoabsorption cross-section is not the only parameter in explaining relative signal intensity, but that solvent photo-ion chemistry can also play a significant role. Three conclusions from this investigation are: (i) Methanol photoionization leads to protonated methanol clusters that can result in chemical ionization of analyte molecule; (ii) Use of the Ar lamp often results in greater signal and S/N; (iii) Acetonitrile photoionization is less efficient and resulting clusters are too strongly bound to efficiently chemically ionize the analyte, so that analyte ion formation is dominated by direct photoionization. PMID:17188507

APPI-MS: effects of mobile phases and VUV lamps on the detection of PAH compounds.

PubMed

Short, Luke Chandler; Cai, Sheng-Suan; Syage, Jack A

2007-04-01

The technique of atmospheric pressure photoionization (APPI) has several advantages over electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), including efficient ionization of nonpolar or low charge affinity compounds, reduced susceptibility to ion suppression, high sensitivity, and large linear dynamic range. These benefits are greatest at low flow rates (i.e.,

The updated bottom up solution applied to atmospheric pressure photoionization and electrospray ionization mass spectrometry

USDA-ARS?s Scientific Manuscript database

The Updated Bottom Up Solution (UBUS) was recently applied to atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) of triacylglycerols (TAGs). This report demonstrates that the UBUS applies equally well to atmospheric pressure photoionization (APPI) MS and to electrospray ionizatio...

A new dynamical atmospheric ionizing radiation (AIR) model for epidemiological studies

NASA Technical Reports Server (NTRS)

De Angelis, G.; Clem, J. M.; Goldhagen, P. E.; Wilson, J. W.

2003-01-01

A new Atmospheric Ionizing Radiation (AIR) model is currently being developed for use in radiation dose evaluation in epidemiological studies targeted to atmospheric flight personnel such as civilian airlines crewmembers. The model will allow computing values for biologically relevant parameters, e.g. dose equivalent and effective dose, for individual flights from 1945. Each flight is described by its actual three dimensional flight profile, i.e. geographic coordinates and altitudes varying with time. Solar modulated primary particles are filtered with a new analytical fully angular dependent geomagnetic cut off rigidity model, as a function of latitude, longitude, arrival direction, altitude and time. The particle transport results have been obtained with a technique based on the three-dimensional Monte Carlo transport code FLUKA, with a special procedure to deal with HZE particles. Particle fluxes are transformed into dose-related quantities and then integrated all along the flight path to obtain the overall flight dose. Preliminary validations of the particle transport technique using data from the AIR Project ER-2 flight campaign of measurements are encouraging. Future efforts will deal with modeling of the effects of the aircraft structure as well as inclusion of solar particle events. Published by Elsevier Ltd on behalf of COSPAR.

A comparative study of APLI and APCI in IMS at atmospheric pressure to reveal and explain peak broadening effects by the use of APLI.

PubMed

Ihlenborg, Marvin; Raupers, Björn; Gunzer, Frank; Grotemeyer, Jürgen

2015-11-21

The details of the ionization mechanism in atmospheric pressure are still not completely known. In order to obtain further insight into the occurring processes in atmospheric pressure laser ionization (APLI) a comparative study of atmospheric pressure chemical ionization (APCI) and APLI is presented in this paper. This study is carried out using similar experimental condition at atmospheric pressure employing a commercial ion mobility spectrometer (IMS). Two different peak broadening mechanisms can then be assigned, one related to a range of different species generated and detected, and furthermore for the first time a power broadening effect on the signals can be identified.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization.

PubMed

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed. Graphical Abstract ᅟ.

Atmospheric Pressure Ionization Using a High Voltage Target Compared to Electrospray Ionization

NASA Astrophysics Data System (ADS)

Lubin, Arnaud; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip

2017-02-01

A new atmospheric pressure ionization (API) source, viz. UniSpray, was evaluated for mass spectrometry (MS) analysis of pharmaceutical compounds by head-to-head comparison with electrospray ionization (ESI) on the same high-resolution MS system. The atmospheric pressure ionization source is composed of a grounded nebulizer spraying onto a high voltage, cylindrical stainless steel target. Molecules are ionized in a similar fashion to electrospray ionization, predominantly producing protonated or deprotonated species. Adduct formation (e.g., proton and sodium adducts) and in-source fragmentation is shown to be almost identical between the two sources. The performance of the new API source was compared with electrospray by infusion of a mix of 22 pharmaceutical compounds with a wide variety of functional groups and physico-chemical properties (molecular weight, logP, and pKa) in more than 100 different conditions (mobile phase strength, solvents, pH, and flow rate). The new API source shows an intensity gain of a factor 2.2 compared with ESI considering all conditions on all compounds tested. Finally, some hypotheses on the ionization mechanism, similarities, and differences with ESI, are discussed.

Plasma Ion Sources for Atmospheric Pressure Ionization Mass Spectrometry.

NASA Astrophysics Data System (ADS)

Zhao, Jian-Guo

1994-01-01

Atmospheric pressure ionization (API) sources using direct-current (DC) and radio-frequency (RF) plasma have been developed in this thesis work. These ion sources can provide stable discharge currents of ~ 1 mA, 2-3 orders of magnitude larger than that of the corona discharge, a widely used API source. The plasmas can be generated and maintained in 1 atm of various buffer gases by applying -500 to -1000 V (DC plasma) or 1-15 W with a frequency of 165 kHz (RF plasma) on the needle electrode. These ion sources have been used with liquid injection to detect various organic compounds of pharmaceutical, biotechnological and environmental interest. Key features of these ion sources include soft ionization with the protonated molecule as the largest peak, and superb sensitivity with detection limits in the low picogram or femtomole range and a linear dynamic range over ~4 orders of magnitude. The RF plasma has advantages over the DC plasma in its ability to operate in various buffer gases and to produce a more stable plasma. Factors influencing the performance of the ion sources have been studied, including RF power level, liquid flow rate, chamber temperature, solvent composition, and voltage affecting the collision induced dissociation (CID). Ionization of hydrocarbons by the RF plasma API source was also studied. Soft ionization is generally produced. To obtain high sensitivity, the ion source must be very dry and the needle-to-orifice distance must be small. Nitric oxide was used to enhance the sensitivity. The RF plasma source was then used for the analysis of hydrocarbons in auto emissions. Comparisons between the corona discharge and the RF plasma have been made in terms of discharge current, ion residence time, and the ion source model. The RF plasma source provides larger linear dynamic range and higher sensitivity than the corona discharge, due to its much larger discharge current. The RF plasma was also observed to provide longer ion residence times and was not limited by space-charge effect as in the corona source.

Influence of Dust Loading on Atmospheric Ionizing Radiation on Mars

NASA Technical Reports Server (NTRS)

Norman, Ryan B.; Gronoff, Guillaume; Mertens, Christopher J.

2014-01-01

Measuring the radiation environment at the surface of Mars is the primary goal of the Radiation Assessment Detector on the NASA Mars Science Laboratory's Curiosity rover. One of the conditions that Curiosity will likely encounter is a dust storm. The objective of this paper is to compute the cosmic ray ionization in different conditions, including dust storms, as these various conditions are likely to be encountered by Curiosity at some point. In the present work, the Nowcast of Atmospheric Ionizing Radiation for Aviation Safety model, recently modified for Mars, was used along with the Badhwar & O'Neill 2010 galactic cosmic ray model. In addition to galactic cosmic rays, five different solar energetic particle event spectra were considered. For all input radiation environments, radiation dose throughout the atmosphere and at the surface was investigated as a function of atmospheric dust loading. It is demonstrated that for galactic cosmic rays, the ionization depends strongly on the atmosphere profile. Moreover, it is shown that solar energetic particle events strongly increase the ionization throughout the atmosphere, including ground level, and can account for the radio blackout conditions observed by the Mars Advanced Radar for Subsurface and Ionospheric Sounding instrument on the Mars Express spacecraft. These results demonstrate that the cosmic rays' influence on the Martian surface chemistry is strongly dependent on solar and atmospheric conditions that should be taken into account for future studies.

Modeling of the initiation and evolution of a laser-ionized column in the lower atmosphere - 314.5 nm wavelength resonant multiphoton ionization of naturally occurring argon

NASA Technical Reports Server (NTRS)

Fetzer, G. J.; Stockley, J. E.

1992-01-01

A 3+1 resonant multiphoton ionization process in naturally occurring argon is studied at 314.5 nm as a candidate for providing a long ionized channel through the atmosphere. Results are presented which indicate peak electron densities up to 10 exp 8/cu cm can be created using laser intensities on the order of 10 exp 8 W/sq cm.

Capillary atmospheric pressure electron capture ionization (cAPECI): a highly efficient ionization method for nitroaromatic compounds.

PubMed

Derpmann, Valerie; Mueller, David; Bejan, Iustinian; Sonderfeld, Hannah; Wilberscheid, Sonja; Koppmann, Ralf; Brockmann, Klaus J; Benter, Thorsten

2014-03-01

We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2(-) or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2(-) leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry.

Atmospheric Gaseous Plasma with Large Dimensions

NASA Astrophysics Data System (ADS)

Korenev, Sergey

2012-10-01

The forming of atmospheric plasma with large dimensions using electrical discharge typically uses the Dielectric Barrier Discharge (DBD). The study of atmospheric DBD was shown some problems related to homogeneous volume plasma. The volume of this plasma determines by cross section and gas gap between electrode and dielectric. The using of electron beam for volume ionization of air molecules by CW relativistic electron beams was shown the high efficiency of this process [1, 2]. The main advantage of this approach consists in the ionization of gas molecules by electrons in longitudinal direction determines by their kinetic energy. A novel method for forming of atmospheric homogeneous plasma with large volume dimensions using ionization of gas molecules by pulsed non-relativistic electron beams is presented in the paper. The results of computer modeling for delivered doses of electron beams in gases and ionization are discussed. The structure of experimental bench with plasma diagnostics is considered. The preliminary results of forming atmospheric plasma with ionization gas molecules by pulsed nanosecond non-relativistic electron beam are given. The analysis of potential applications for atmospheric volume plasma is presented. Reference: [1] S. Korenev. ``The ionization of air by scanning relativistic high power CW electron beam,'' 2002 IEEE International Conference on Plasma Science. May 2002, Alberta, Canada. [2] S. Korenev, I. Korenev. ``The propagation of high power CW scanning electron beam in air.'' BEAMS 2002: 14th International Conference on High-Power Particle Beams, Albuquerque, New Mexico (USA), June 2002, AIP Conference Proceedings Vol. 650(1), pp. 373-376. December 17.

Atmospheric changes caused by galactic cosmic rays over the period 1960–2010

DOE PAGES

Jackman, Charles H.; Marsh, Daniel R.; Kinnison, Douglas E.; ...

2016-05-13

The Specified Dynamics version of the Whole Atmosphere Community Climate Model (SD-WACCM) and the Goddard Space Flight Center two-dimensional (GSFC 2-D) models are used to investigate the effect of galactic cosmic rays (GCRs) on the atmosphere over the 1960–2010 time period. The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) computation of the GCR-caused ionization rates are used in these simulations. GCR-caused maximum NO x increases of 4–15 % are computed in the Southern polar troposphere with associated ozone increases of 1–2 %. NO x increases of ~1–6 % are calculated for the lower stratosphere with associated ozone decreasesmore » of 0.2–1 %. The primary impact of GCRs on ozone was due to their production of NO x. The impact of GCRs varies with the atmospheric chlorine loading, sulfate aerosol loading, and solar cycle variation. Because of the interference between the NO x and ClO x ozone loss cycles (e.g., the ClO + NO 2+ M → ClONO 2+ M reaction) and the change in the importance of ClO x in the ozone budget, GCRs cause larger atmospheric impacts with less chlorine loading. GCRs also cause larger atmospheric impacts with less sulfate aerosol loading and for years closer to solar minimum. GCR-caused decreases of annual average global total ozone (AAGTO) were computed to be 0.2 % or less with GCR-caused column ozone increases between 1000 and 100 hPa of 0.08 % or less and GCR-caused column ozone decreases between 100 and 1 hPa of 0.23 % or less. Although these computed ozone impacts are small, GCRs provide a natural influence on ozone and need to be quantified over long time periods. This result serves as a lower limit because of the use of the ionization model NAIRAS/HZETRN which underestimates the ion production by neglecting electromagnetic and muon branches of the cosmic ray induced cascade. Furthermore, this will be corrected in future works.« less

Atmospheric changes caused by galactic cosmic rays over the period 1960–2010

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jackman, Charles H.; Marsh, Daniel R.; Kinnison, Douglas E.

The Specified Dynamics version of the Whole Atmosphere Community Climate Model (SD-WACCM) and the Goddard Space Flight Center two-dimensional (GSFC 2-D) models are used to investigate the effect of galactic cosmic rays (GCRs) on the atmosphere over the 1960–2010 time period. The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) computation of the GCR-caused ionization rates are used in these simulations. GCR-caused maximum NO x increases of 4–15 % are computed in the Southern polar troposphere with associated ozone increases of 1–2 %. NO x increases of ~1–6 % are calculated for the lower stratosphere with associated ozone decreasesmore » of 0.2–1 %. The primary impact of GCRs on ozone was due to their production of NO x. The impact of GCRs varies with the atmospheric chlorine loading, sulfate aerosol loading, and solar cycle variation. Because of the interference between the NO x and ClO x ozone loss cycles (e.g., the ClO + NO 2+ M → ClONO 2+ M reaction) and the change in the importance of ClO x in the ozone budget, GCRs cause larger atmospheric impacts with less chlorine loading. GCRs also cause larger atmospheric impacts with less sulfate aerosol loading and for years closer to solar minimum. GCR-caused decreases of annual average global total ozone (AAGTO) were computed to be 0.2 % or less with GCR-caused column ozone increases between 1000 and 100 hPa of 0.08 % or less and GCR-caused column ozone decreases between 100 and 1 hPa of 0.23 % or less. Although these computed ozone impacts are small, GCRs provide a natural influence on ozone and need to be quantified over long time periods. This result serves as a lower limit because of the use of the ionization model NAIRAS/HZETRN which underestimates the ion production by neglecting electromagnetic and muon branches of the cosmic ray induced cascade. Furthermore, this will be corrected in future works.« less

Highly sensitive screening method for nitroaromatic, nitramine and nitrate ester explosives by high performance liquid chromatography-atmospheric pressure ionization-mass spectrometry (HPLC-API-MS) in forensic applications.

PubMed

Xu, Xiaoma; van de Craats, Anick M; de Bruyn, Peter C A M

2004-11-01

A highly sensitive screening method based on high performance liquid chromatography atmospheric pressure ionization mass spectrometry (HPLC-API-MS) has been developed for the analysis of 21 nitroaromatic, nitramine and nitrate ester explosives, which include the explosives most commonly encountered in forensic science. Two atmospheric pressure ionization (API) methods, atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI), and various experimental conditions have been applied to allow for the detection of all 21 explosive compounds. The limit of detection (LOD) in the full-scan mode has been found to be 0.012-1.2 ng on column for the screening of most explosives investigated. For nitrobenzene, an LOD of 10 ng was found with the APCI method in the negative mode. Although the detection of nitrobenzene, 2-, 3-, and 4-nitrotoluene is hindered by the difficult ionization of these compounds, we have found that by forming an adduct with glycine, LOD values in the range of 3-16 ng on column can be achieved. Compared with previous screening methods with thermospray ionization, the API method has distinct advantages, including simplicity and stability of the method applied, an extended screening range and a low detection limit for the explosives studied.

Atmospheric Ionization Measurements

NASA Astrophysics Data System (ADS)

Slack, Thomas; Mayes, Riley

2015-04-01

The measurement of atmospheric ionization is a largely unexplored science that potentially holds the key to better understanding many different geophysical phenomena through this new and valuable source of data. Through the LaACES program, which is funded by NASA through the Louisiana Space Consortium, students at Loyola University New Orleans have pursued the goal of measuring high altitude ionization for nearly three years, and were the first to successfully collect ionization data at altitudes over 30,000 feet using a scientific weather balloon flown from the NASA Columbia Scientific Ballooning Facility in Palestine, TX. In order to measure atmospheric ionization, the science team uses a lightweight and highly customized sensor known as a Gerdien condenser. Among other branches of science the data is already being used for, such as the study of aerosol pollution levels in the atmosphere, the data may also be useful in meteorology and seismology. Ionization data might provide another variable with which to predict weather or seismic activity more accurately and further in advance. Thomas Slack and Riley Mayes have served as project managers for the experiment, and have extensive knowledge of the experiment from the ground up. LaSPACE Louisiana Space Consortium.

Role of the ionosphere for the atmospheric evolution of planets.

PubMed

Yamauchi, Masatoshi; Wahlund, Jan-Erik

2007-10-01

We have synthesized current understanding, mainly observations, with regard to ion escape mechanisms to space from the ionosphere and exosphere of Titan and Earth-type planets, with the intent to provide an improved input for models of atmospheric evolution on early Earth and Earth-type planets and exoplanets. We focus on the role of the ionosphere and its non-linear response to solar parameters, all of which have been underestimated in current models of ancient atmospheric escape (4 billion years ago). Factors that have been overlooked include the following: (1) Much larger variation of O(+) outflow than H(+) outflow from the terrestrial ionosphere, depending on solar and geomagnetic activities (an important consideration when attempting to determine the oxidized state of the atmosphere of early Earth); (2) magnetization of the ionopause, which keeps ionospheric ions from escaping and controls many other escape processes; (3) extra ionization by, for example, the critical ionization velocity mechanism, which expands the ionosphere to greater altitudes than current models predict; and (4) the large escape of cold ions from the dense, expanded ionosphere of Titan. Here we offer, as a guideline for quantitative simulations, a qualitative diagnosis of increases or decreases of non-thermal escape related to the ionosphere for magnetized and unmagnetized planets in response to changes in solar parameters (i.e., solar EUV/FUV flux, solar wind dynamic pressure, and interplanetary magnetic field).

A Massively Parallel Particle Code for Rarefied Ionized and Neutral Gas Flows in Earth and Planetary Atmospheres, Ionospheres and Magnetospheres

NASA Technical Reports Server (NTRS)

Combi, Michael R.

2004-01-01

In order to understand the global structure, dynamics, and physical and chemical processes occurring in the upper atmospheres, exospheres, and ionospheres of the Earth, the other planets, comets and planetary satellites and their interactions with their outer particles and fields environs, it is often necessary to address the fundamentally non-equilibrium aspects of the physical environment. These are regions where complex chemistry, energetics, and electromagnetic field influences are important. Traditional approaches are based largely on hydrodynamic or magnetohydrodynamic MHD) formulations and are very important and highly useful. However, these methods often have limitations in rarefied physical regimes where the molecular collision rates and ion gyrofrequencies are small and where interactions with ionospheres and upper neutral atmospheres are important.

The Role of Helium Metastable States in Radio-Frequency Helium-Oxygen Atmospheric Pressure Plasma Jets: Measurement and Numerical Simulation

NASA Astrophysics Data System (ADS)

Niemi, Kari; Waskoenig, Jochen; Sadeghi, Nader; Gans, Timo; O'Connell, Deborah

2011-10-01

Absolute densities of metastable He atoms were measured line-of sight integrated along the plasma channel of a capacitively-coupled radio-frequency driven atmospheric pressure plasma jet operated in helium oxygen mixtures by tunable diode-laser absorption spectroscopy. Dependencies of the He metastable density with oxygen admixtures up to 1 percent were investigated. Results are compared to a 1-d numerical simulation, which includes a semi-kinetical treatment of the electron dynamics and the complex plasma chemistry (20 species, 184 reactions), and very good agreement is found. The main formation mechanisms for the helium metastables are identified and analyzed, including their pronounced spatio-temporal dynamics. Penning ionization through helium metastables is found to be significant for plasma sustainment, while it is revealed that helium metastables are not an important energy carrying species into the jet effluent and therefore will not play a direct role in remote surface treatments.

Ionization Processes in the Atmosphere of Titan (Research Note). III. Ionization by High-Z Nuclei Cosmic Rays

NASA Technical Reports Server (NTRS)

Gronoff, G.; Mertens, C.; Lilensten, J.; Desorgher, L.; Fluckiger, E.; Velinov, P.

2011-01-01

Context. The Cassini-Huygens mission has revealed the importance of particle precipitation in the atmosphere of Titan thanks to in-situ measurements. These ionizing particles (electrons, protons, and cosmic rays) have a strong impact on the chemistry, hence must be modeled. Aims. We revisit our computation of ionization in the atmosphere of Titan by cosmic rays. The high-energy high-mass ions are taken into account to improve the precision of the calculation of the ion production profile. Methods. The Badhwahr and O Neill model for cosmic ray spectrum was adapted for the Titan model. We used the TransTitan model coupled with the Planetocosmics model to compute the ion production by cosmic rays. We compared the results with the NAIRAS/HZETRN ionization model used for the first time for a body that differs from the Earth. Results. The cosmic ray ionization is computed for five groups of cosmic rays, depending on their charge and mass: protons, alpha, Z = 8 (oxygen), Z = 14 (silicon), and Z = 26 (iron) nucleus. Protons and alpha particles ionize mainly at 65 km altitude, while the higher mass nucleons ionize at higher altitudes. Nevertheless, the ionization at higher altitude is insufficient to obscure the impact of Saturn s magnetosphere protons at a 500 km altitude. The ionization rate at the peak (altitude: 65 km, for all the different conditions) lies between 30 and 40/cu cm/s. Conclusions. These new computations show for the first time the importance of high Z cosmic rays on the ionization of the Titan atmosphere. The updated full ionization profile shape does not differ significantly from that found in our previous calculations (Paper I: Gronoff et al. 2009, 506, 955) but undergoes a strong increase in intensity below an altitude of 400 km, especially between 200 and 400 km altitude where alpha and heavier particles (in the cosmic ray spectrum) are responsible for 40% of the ionization. The comparison of several models of ionization and cosmic ray spectra (in intensity and composition) reassures us about the stability of the altitude of the ionization peak (65 km altitude) with respect to the solar activity.

The sensibility of SPE induced atmospheric photochemical response to the ionization rate variations.

NASA Astrophysics Data System (ADS)

Krivolutsky, Alexei A.; Kukoleva, Anna; Kuminov, Alexander; Maygkova, Irina

During Solar proton event (SPE) energetic particles affect neutral atmospheric chemistry (Jackman et al. 1990, Krivolutsky A.A. et al. 2001 ets. ). The calculations results for [NO] and [O3] changes have qualitative suitability with observations data from satellites (UARS, HALOE for N.P.), although the simulated result differs in value from observed ones for nitrogen compounds. It seems potential probable reasons for this diversity exist. The sensibility of SPE induced atmospheric response to the ionization rates was investigated. The solar proton fluxes data from two satellites were used for ionization rate calculations by the method Vitt and Jackman (1996): geo-stationary GOES-10 (orbit height ≈ 40000 km) and CORONAS (orbit height is ≈ 400 km) for period of SPE 28.10. 2003. Calculated time integral ion creation during SPE using low and high orbit data differs for 1.5. Differences in ionization rate vertical distribution from GOES and CORONAS were found. Using this different ionization data the atmospherical composition response has been simulated with 1D photochemical model. The corresponding differences are discussed.

The solar-terrestrial environment. An introduction to geospace - the science of the terrestrial upper atmosphere, ionosphere and magnetosphere.

NASA Astrophysics Data System (ADS)

Hargreaves, J. K.

This textbook is a successor to "The upper atmosphere and solar-terrestrial relations" first published in 1979. It describes physical conditions in the upper atmosphere and magnetosphere of the Earth. This geospace environment begins 70 kilometres above the surface of the Earth and extends in near space to many times the Earth's radius. It is the region of near-Earth environment where the Space Shuttle flies, the aurora is generated, and the outer atmosphere meets particles streaming out of the sun. The account is introductory. The intent is to present basic concepts, and for that reason the mathematical treatment is not complex. There are three introductory chapters that give basic physics and explain the principles of physical investigation. The principal material contained in the main part of the book covers the neutral and ionized upper atmosphere, the magetosphere, and structures, dynamics, disturbances and irregularities. The concluding chapter deals with technological applications.

Source of Global Scale Variations in the Midday Vertical Content of Ionospheric Metal Ions

NASA Technical Reports Server (NTRS)

Joiner, J.; Grebowsky, J. M.; Pesnell, W. D.; Aikin, A. C.; Goldberg, Richard A.

1999-01-01

An analysis of long baseline NIMBUS 7 SBUV (Solar Backscatter UV Spectrometer) observations of the latitudinal variation of the noontime vertical Mg' content above approx. 70 km have revealed seasonal, solar activity and magnetic activity dependencies in the Mg+ content. The distributions were categorized in terms of magnetic coordinates partially because transport processes lifting metallic ions from the main meteor ionization layer below 100 km up into the F- region and down again are controlled by electrodynamical processes. Alternatively, the Nimbus Mg+ distributions may simply be a result of ion/neutral chemistry changes resulting from atmospheric changes and not dynamics. In such a case magnetic control would not dominate the distributions. Using in situ satellite measurements of metal ions from the Atmosphere Explorer satellites in the region above the main meteor layer and published sounding rocket measurements of the main metallic ion layers, the effects of the dynamics on the vertical content are delineated. The consequences of atmospheric changes on the vertical content are explored by separating the Nimbus measurements in a geodetic frame of reference.

Quality classification of Spanish olive oils by untargeted gas chromatography coupled to hybrid quadrupole-time of flight mass spectrometry with atmospheric pressure chemical ionization and metabolomics-based statistical approach.

PubMed

Sales, C; Cervera, M I; Gil, R; Portolés, T; Pitarch, E; Beltran, J

2017-02-01

The novel atmospheric pressure chemical ionization (APCI) source has been used in combination with gas chromatography (GC) coupled to hybrid quadrupole time-of-flight (QTOF) mass spectrometry (MS) for determination of volatile components of olive oil, enhancing its potential for classification of olive oil samples according to their quality using a metabolomics-based approach. The full-spectrum acquisition has allowed the detection of volatile organic compounds (VOCs) in olive oil samples, including Extra Virgin, Virgin and Lampante qualities. A dynamic headspace extraction with cartridge solvent elution was applied. The metabolomics strategy consisted of three different steps: a full mass spectral alignment of GC-MS data using MzMine 2.0, a multivariate analysis using Ez-Info and the creation of the statistical model with combinations of responses for molecular fragments. The model was finally validated using blind samples, obtaining an accuracy in oil classification of 70%, taking the official established method, "PANEL TEST", as reference. Copyright © 2016 Elsevier Ltd. All rights reserved.

Overview of our current understanding of the Titan ionosphere

NASA Astrophysics Data System (ADS)

Cravens, Thomas

An ionosphere was first detected on Titan in 1980 by the Voyager 1 radio occultation experi-ment and the first in situ measurements were made in 2004 by the Cassini spacecraft, although many theoretical studies were carried out prior to the Cassini mission. Earth and Titan are similar in that molecular nitrogen is the major neutral atmospheric species but these bodies differ in that the next most abundant species at Earth is molecular oxygen and at Titan is methane. As a consequence, the chemistry in the upper atmosphere and ionosphere is quite different for the two bodies. Titan's upper atmosphere and ionosphere strongly interact with Saturn's magnetospheric plasma. Magnetic fields were observed in Titan's ionosphere by the Cassini magnetometer and are induced as a consequence of this interaction, which affects the flow and distribution of plasma. Energetic electrons and ions from Saturn's magnetosphere precipitate into the upper atmosphere, acting as both heat and ionization sources. However, on the dayside, absorption of solar extreme ultraviolet radiation is thought to be the dominant source of ionization and energy. The electron temperatures measured in the ionosphere by the Cassini Langmuir probe (RPWS/LP) are about 1000 K, greatly exceeding the neutral temper-ature (about 150 K). The ion and neutral mass spectrometer (INMS) onboard Cassini detected a large number of ion species with mass numbers up to 100 Daltons and the energetic plasma spectrometer (CAPS) detected both negative and positive ion species at even higher mass num-bers. Primary ionization processes create N2+, N+, CH4+, CH3+, and other ion species, but a complex ion-neutral chemistry, involving methane and other hydrocarbon and nitriles species (acetylene, ethylene, ethane, hydrogen cyanide, benzene,. . . .), convert these initial species into numerous other species including CH5+, C2H5+, HCNH+, C3H5+, CH2NH2+, C6H7+. As in most ionospheres, chemistry dominates the ionospheric structure at lower altitudes but trans-port is more important at higher altitudes. Just at at Venus during higher dynamics pressure solar wind conditions, the magnetic field plays a key role in the ionospheric dynamics at Titan but neutral winds also contribute to the flow of plasma. This talk will provide an overview of observations of Titan's ionosphere and will also review the physical and chemical processes operating in this ionosphere.

The Solar-Terrestrial Environment

NASA Astrophysics Data System (ADS)

Hargreaves, John Keith

1995-05-01

The book begins with three introductory chapters that provide some basic physics and explain the principles of physical investigation. The principal material contained in the main part of the book covers the neutral and ionized upper atmosphere, the magnetosphere, and structures, dynamics, disturbances, and irregularities. The concluding chapter deals with technological applications. The account is introductory, at a level suitable for readers with a basic background in engineering or physics. The intent is to present basic concepts, and for that reason, the mathematical treatment is not complex. SI units are given throughout, with helpful notes on cgs units where these are likely to be encountered in the research literature. This book is suitable for advanced undergraduate and graduate students who are taking introductory courses on upper atmospheric, ionospheric, or magnetospheric physics. This is a successor to The Upper Atmosphere and Solar-Terrestrial Relations, published in 1979.

Mass spectrometry for water vapor measurements in the UT/LS

NASA Astrophysics Data System (ADS)

Kaufmann, S.; Voigt, C.; Schäuble, D.; Schäfler, A.; Schlager, H.; Thornberry, T. D.; Fahey, D. W.

2012-12-01

Water vapor in the lower stratosphere plays a crucial role for the atmospheric radiation budget (Solomon et al., 2011). However, large uncertainties remain in measuring atmospheric water vapor mixing ratios below 10 ppmv typical for the lower stratosphere. To this end, we have developed the Atmospheric Ionization Mass Spectrometer (AIMS) for the accurate and fast detection of water vapor in the UT/LS from aircraft. In the AIMS instrument atmospheric air is directly ionized in a discharge ion source and the resulting water vapor clusters H3O+(H2O)n (n = 0..3) are detected with a linear quadrupole mass spectrometer as a direct measure of the atmospheric water vapor mixing ratio. AIMS is calibrated in-flight with a H2O calibration source using the catalytic reaction of H2 and O2 on a heated platinum surface to form gaseous H2O. This calibration setup combined with the water vapor mass spectrometry offers a powerful technical development in atmospheric hygrometry, enriching existing H2O measurement techniques by a new independent method. Here, we present AIMS water vapor measurements performed during the CONCERT2011 campaign (Contrail and Cirrus Experiment) with the DLR research aircraft Falcon. In September 2011 a deep stratospheric intrusion was probed over northern Europe with a dynamical tropopause lowered down to 6 km. We found sharp humidity gradients between tropospheric and stratospheric air at the edge of the tropopause fold, which we crossed 4 times at altitudes between 6 and 11 km. In the center of the tropopause fold, we measured water vapor mixing ratios down to 4 ppmv. The observed water vapor distribution is compared to water vapor analysis fields of the ECMWF's Integrated Forecast System (IFS) to evaluate the representation water vapor in this specific meteorological situation.

The role of partial ionization effects in the chromosphere

PubMed Central

Martínez-Sykora, Juan; De Pontieu, Bart; Hansteen, Viggo; Carlsson, Mats

2015-01-01

The energy for the coronal heating must be provided from the convection zone. However, the amount and the method by which this energy is transferred into the corona depend on the properties of the lower atmosphere and the corona itself. We review: (i) how the energy could be built in the lower solar atmosphere, (ii) how this energy is transferred through the solar atmosphere, and (iii) how the energy is finally dissipated in the chromosphere and/or corona. Any mechanism of energy transport has to deal with the various physical processes in the lower atmosphere. We will focus on a physical process that seems to be highly important in the chromosphere and not deeply studied until recently: the ion–neutral interaction effects in the chromosphere. We review the relevance and the role of the partial ionization in the chromosphere and show that this process actually impacts considerably the outer solar atmosphere. We include analysis of our 2.5D radiative magnetohydrodynamic simulations with the Bifrost code (Gudiksen et al. 2011 Astron. Astrophys. 531, A154 (doi:10.1051/0004-6361/201116520)) including the partial ionization effects on the chromosphere and corona and thermal conduction along magnetic field lines. The photosphere, chromosphere and transition region are partially ionized and the interaction between ionized particles and neutral particles has important consequences on the magneto-thermodynamics of these layers. The partial ionization effects are treated using generalized Ohm's law, i.e. we consider the Hall term and the ambipolar diffusion (Pedersen dissipation) in the induction equation. The interaction between the different species affects the modelled atmosphere as follows: (i) the ambipolar diffusion dissipates magnetic energy and increases the minimum temperature in the chromosphere and (ii) the upper chromosphere may get heated and expanded over a greater range of heights. These processes reveal appreciable differences between the modelled atmospheres of simulations with and without ion–neutral interaction effects. PMID:25897096

Mass spectrometry imaging for visualizing organic analytes in food.

PubMed

Handberg, Eric; Chingin, Konstantin; Wang, Nannan; Dai, Ximo; Chen, Huanwen

2015-01-01

The demand for rapid chemical imaging of food products steadily increases. Mass spectrometry (MS) is featured by excellent molecular specificity of analysis and is, therefore, a very attractive method for chemical profiling. MS for food imaging has increased significantly over the past decade, aided by the emergence of various ambient ionization techniques that allow direct and rapid analysis in ambient environment. In this article, the current status of food imaging with MSI is reviewed. The described approaches include matrix-assisted laser desorption/ionization (MALDI), but emphasize desorption atmospheric pressure photoionization (DAPPI), electrospray-assisted laser desorption/ionization (ELDI), probe electrospray ionization (PESI), surface desorption atmospheric pressure chemical ionization (SDAPCI), and laser ablation flowing atmospheric pressure afterglow (LA-FAPA). The methods are compared with regard to spatial resolution; analysis speed and time; limit of detection; and technical aspects. The performance of each method is illustrated with the description of a related application. Specific requirements in food imaging are discussed. © 2014 Wiley Periodicals, Inc.

Fundamentals of ambient metastable-induced chemical ionization mass spectrometry and atmospheric pressure ion mobility spectrometry

NASA Astrophysics Data System (ADS)

Harris, Glenn A.

Molecular ionization is owed much of its development from the early implementation of electron ionization (EI). Although dramatically increasing the library of compounds discovered, an inherent problem with EI was the low abundance of molecular ions detected due to high fragmentation leading to the difficult task of the correct chemical identification after mass spectrometry (MS). These problems stimulated the research into new ionization methods which sought to "soften" the ionization process. In the late 1980s the advancements of ionization techniques was thought to have reached its pinnacle with both electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI). Both ionization techniques allowed for "soft" ionization of large molecular weight and/or labile compounds for intact characterization by MS. Albeit pervasive, neither ESI nor MALDI can be viewed as "magic bullet" ionization techniques. Both techniques require sample preparation which often included native sample destruction, and operation of these techniques took place in sealed enclosures and often, reduced pressure conditions. New open-air ionization techniques termed "ambient MS" enable direct analysis of samples of various physical states, sizes and shapes. One particular technique named Direct Analysis In Real Time (DART) has been steadily growing as one of the ambient tools of choice to ionize small molecular weight (< 1000 Da) molecules with a wide range of polarities. Although there is a large list of reported applications using DART as an ionization source, there have not been many studies investigating the fundamental properties of DART desorption and ionization mechanisms. The work presented in this thesis is aimed to provide in depth findings on the physicochemical phenomena during open-air DART desorption and ionization MS and current application developments. A review of recent ambient plasma-based desorption/ionization techniques for analytical MS is presented in Chapter 1. Chapter 2 presents the first investigations into the atmospheric pressure ion transport phenomena during DART analysis. Chapter 3 provides a comparison on the internal energy deposition processes during DART and pneumatically assisted-ESI. Chapter 4 investigates the complex spatially-dependent sampling sensitivity, dynamic range and ion suppression effects present in most DART experiments. New implementations and applications with DART are shown in Chapters 5 and 6. In Chapter 5, DART is coupled to multiplexed drift tube ion mobility spectrometry as a potential fieldable platform for the detection of toxic industrial chemicals and chemical warfare agents simulants. In Chapter 6, transmission-mode DART is shown to be an effective method for reproducible sampling from materials which allow for gas to flow through it. Also, Chapter 6 provides a description of a MS imaging platform coupling infrared laser ablation and DART-like phenomena. Finally, in Chapter 7 I will provide perspective on the work completed with DART and the tasks and goals that future studies should focus on.

Mechanism of Runaway Electron Generation at Gas Pressures from a Few Atmospheres to Several Tens of Atmospheres

NASA Astrophysics Data System (ADS)

Zubarev, N. M.; Ivanov, S. N.

2018-04-01

The mechanism of runaway electron generation at gas pressures from a few atmospheres to several tens of atmospheres is proposed. According to this mechanism, the electrons pass into the runaway mode in the enhanced field zone that arises between a cathode micropoint—a source of field-emission electrons—and the region of the positive ion space charge accumulated near the cathode in the tails of the developing electron avalanches. As a result, volume gas ionization by runaway electrons begins with a time delay required for the formation of the enhanced field zone. This process determines the delay time of breakdown. The influence of the gas pressure on the formation dynamics of the space charge region is analyzed. At gas pressures of a few atmospheres, the space charge arises due to the avalanche multiplication of the very first field-emission electron, whereas at pressures of several tens of atmospheres, the space charge forms as a result of superposition of many electron avalanches with a relatively small number of charge carriers in each.

Ionization ratios and elemental abundances in the atmosphere of 68 Tauri

NASA Astrophysics Data System (ADS)

Aouina, A.; Monier, R.

2017-12-01

We have derived the ionization ratios of twelve elements in the atmosphere of the star 68 Tauri (HD 27962) using an ATLAS9 model atmosphere with 72 layers computed for the effective temperature and surface gravity of the star. We then computed a grid of synthetic spectra generated by SYNSPEC49 based on an ATLAS9 model atmosphere in order to model one high resolution spectrum secured by one of us (RM) with the échelle spectrograph SOPHIE at Observatoire de Haute Provence. We could determine the abundances of several elements in their dominant ionization stage, including those defining the Am phenomenon. We thus provide new abundance determinations for 68 Tauri using updated accurate atomic data retrieved from the NIST database which extend previous abundance works.

Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations.

PubMed

Klee, Sonja; Derpmann, Valerie; Wißdorf, Walter; Klopotowski, Sebastian; Kersten, Hendrik; Brockmann, Klaus J; Benter, Thorsten; Albrecht, Sascha; Bruins, Andries P; Dousty, Faezeh; Kauppila, Tiina J; Kostiainen, Risto; O'Brien, Rob; Robb, Damon B; Syage, Jack A

2014-08-01

It is well documented since the early days of the development of atmospheric pressure ionization methods, which operate in the gas phase, that cluster ions are ubiquitous. This holds true for atmospheric pressure chemical ionization, as well as for more recent techniques, such as atmospheric pressure photoionization, direct analysis in real time, and many more. In fact, it is well established that cluster ions are the primary carriers of the net charge generated. Nevertheless, cluster ion chemistry has only been sporadically included in the numerous proposed ionization mechanisms leading to charged target analytes, which are often protonated molecules. This paper series, consisting of two parts, attempts to highlight the role of cluster ion chemistry with regard to the generation of analyte ions. In addition, the impact of the changing reaction matrix and the non-thermal collisions of ions en route from the atmospheric pressure ion source to the high vacuum analyzer region are discussed. This work addresses such issues as extent of protonation versus deuteration, the extent of analyte fragmentation, as well as highly variable ionization efficiencies, among others. In Part 1, the nature of the reagent ion generation is examined, as well as the extent of thermodynamic versus kinetic control of the resulting ion population entering the analyzer region.

Detection of lower tropospheric responses to solar energetic particles at midlatitudes.

PubMed

Nicoll, K A; Harrison, R G

2014-06-06

Solar energetic particles (SEPs) occasionally contribute additional atmospheric ionization beyond that arising from the usual galactic cosmic ray background. During an SEP event associated with a solar flare on April 11, 2013, the vertical ionization rate profile obtained using a balloon-borne detector showed enhanced ionization with a 26% increase at 20 km, over Reading, United Kingdom. Fluctuations in atmospheric electrical parameters were also detected at the surface, beneath the balloon's trajectory. As no coincident changes in geomagnetism occurred, the electrical fluctuations are very likely to be associated with increased ionization, as observed by the balloon measurements. The lack of response of surface neutron monitors during this event indicates that energetic particles that are not detected at the surface by neutron monitors can nevertheless enter and influence the atmosphere's weather-generating regions.

Understanding the flowing atmospheric-pressure afterglow (FAPA) ambient ionization source through optical means.

PubMed

Shelley, Jacob T; Chan, George C-Y; Hieftje, Gary M

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H(2)O vapor, N(2), and O(2) diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (T(rot)) and electron number density (n(e)), were also measured in the APGD. Maximum values for T(rot) and n(e) were found to be ~1100 K and ~4×10(19) m(-3), respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N(2)(+) yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N(2)(+) temperature is believed to be caused by charge-transfer ionization of N(2) by He(2)(+). These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source. © American Society for Mass Spectrometry, 2011

Understanding the Flowing Atmospheric-Pressure Afterglow (FAPA) Ambient Ionization Source through Optical Means

NASA Astrophysics Data System (ADS)

Shelley, Jacob T.; Chan, George C.-Y.; Hieftje, Gary M.

2012-02-01

The advent of ambient desorption/ionization mass spectrometry (ADI-MS) has led to the development of a large number of atmospheric-pressure ionization sources. The largest group of such sources is based on electrical discharges; yet, the desorption and ionization processes that they employ remain largely uncharacterized. Here, the atmospheric-pressure glow discharge (APGD) and afterglow of a helium flowing atmospheric-pressure afterglow (FAPA) ionization source were examined by optical emission spectroscopy. Spatial emission profiles of species created in the APGD and afterglow were recorded under a variety of operating conditions, including discharge current, electrode polarity, and plasma-gas flow rate. From these studies, it was found that an appreciable amount of atmospheric H2O vapor, N2, and O2 diffuses through the hole in the plate electrode into the discharge to become a major source of reagent ions in ADI-MS analyses. Spatially resolved plasma parameters, such as OH rotational temperature (Trot) and electron number density (ne), were also measured in the APGD. Maximum values for Trot and ne were found to be ~1100 K and ~4 × 1019 m-3, respectively, and were both located at the pin cathode. In the afterglow, rotational temperatures from OH and N{2/+} yielded drastically different values, with OH temperatures matching those obtained from infrared thermography measurements. The higher N{2/+} temperature is believed to be caused by charge-transfer ionization of N2 by He{2/+}. These findings are discussed in the context of previously reported ADI-MS analyses with the FAPA source.

Current status of the CAWSES-II Task Group 4: What is the geospace response to variable inputs from the lower atmosphere?

NASA Astrophysics Data System (ADS)

Shiokawa, Kazuo; Oberheide, Jens

2012-07-01

Recent developments of coupled modeling between neutral and ionized atmosphere and various observation techniques such as advanced radars, airglow imaging, and GPS networks, make it possible to study geospace response to variable inputs from the lower atmosphere. Consequences for telecommunications, re-entry and satellite operations still need to be explored. The extent to which the effects of this quiescent atmospheric variability are transmitted to the magnetosphere is yet to be resolved. We thus stand right now at an exciting research frontier: understanding the cause-and-effect chain that connects tropospheric and strato-/mesospheric variability with geospace processes. CAWSES-II Task Group 4 (TG4) will therefore elucidate the dynamical coupling from the low and middle atmosphere to the geospace including the upper atmosphere, ionosphere, and magnetosphere, for various frequencies and scales, such as gravity waves, tides, and planetary waves, and for equatorial, middle, and high latitudes. Attacking the problem clearly requires asystems approach involving experimentalists, data analysts and modelers from different communities. For that purpose, the most essential part of TG4 is to encourage interactions between atmospheric scientists and plasma scientists on all occasions. TG4 newsletters are distributed to the related scientists every 3-4 months to introduce various activities of atmospheric and ionospheric researches. Five projects are established in TG4, i.e., Project 1: How do atmospheric waves connect tropospheric weather with ITM variability?, Project 2: What is the relation between atmospheric waves and ionospheric instabilities?, Project 3: How do the different types of waves interact as they propagate through the stratosphere to the ionosphere?, Project 4: How do thermospheric disturbances generated by auroral processes interact with the neutral and ionized atmosphere?, and Project 5: How do thunderstorm activities interact with the atmosphere, ionosphere and magnetosphere? Three campaign observations have been carried out in relation to the TG4 activity, i.e, stratospheric sudden warming campaign (January-February, 2010), longitudinal campaign (September 1-November 12, 2010 and August 22-November 2, 2011), and CAWSES Tidal Campaign. In this presentation we show the current status and future plan of CAWSES-II TG4 activities of 2009-2013.

Effect of a finite ionization rate on the radiative heating of outer planet atmospheric entry probes

NASA Technical Reports Server (NTRS)

Nelson, H. F.

1982-01-01

The influence of finite rate ionization in the inviscid gas just behind the stagnation shock wave on the radiative heating of probes entering the hydrogen-helium atmosphere of the major plants was investigated. Two opposing conclusions were reached as to how the ionization rate assumption affects the radiative transfer. Hydrogen-helium shock waves with a cold nonblowing wall boundary condition at the probe heat shield are emphasized. The study is limited to the stagnation shock layer.

Ionization techniques in capillary electrophoresis-mass spectrometry: principles, design, and application.

PubMed

Hommerson, Paul; Khan, Amjad M; de Jong, Gerhardus J; Somsen, Govert W

2011-01-01

A major step forward in the development and application of capillary electrophoresis (CE) was its coupling to ESI-MS, first reported in 1987. More than two decades later, ESI has remained the principal ionization technique in CE-MS, but a number of other ionization techniques have also been implemented. In this review the state-of-the-art in the employment of soft ionization techniques for CE-MS is presented. First the fundamentals and general challenges of hyphenating conventional CE and microchip electrophoresis with MS are outlined. After elaborating on the characteristics and role of ESI, emphasis is put on alternative ionization techniques including sonic spray ionization (SSI), thermospray ionization (TSI), atmospheric pressure chemical ionization (APCI), atmospheric pressure photoionization (APPI), matrix-assisted laser desorption ionization (MALDI) and continuous-flow fast atom bombardment (CF-FAB). The principle of each ionization technique is outlined and the experimental set-ups of the CE-MS couplings are described. The strengths and limitations of each ionization technique with respect to CE-MS are discussed and the applicability of the various systems is illustrated by a number of typical examples. Copyright © 2011 Wiley Periodicals, Inc.

Influence of hadron and atmospheric models on computation of cosmic ray ionization in the atmosphere-Extension to heavy nuclei

NASA Astrophysics Data System (ADS)

Mishev, A. L.; Velinov, P. I. Y.

2014-12-01

In the last few years an essential progress in development of physical models for cosmic ray induced ionization in the atmosphere is achieved. The majority of these models are full target, i.e. based on Monte Carlo simulation of an electromagnetic-muon-nucleon cascade in the atmosphere. Basically, the contribution of proton nuclei is highlighted, i.e. the contribution of primary cosmic ray α-particles and heavy nuclei to the atmospheric ionization is neglected or scaled to protons. The development of cosmic ray induced atmospheric cascade is sensitive to the energy and mass of the primary cosmic ray particle. The largest uncertainties in Monte Carlo simulations of a cascade in the Earth atmosphere are due to assumed hadron interaction models, the so-called hadron generators. In the work presented here we compare the ionization yield functions Y for primary cosmic ray nuclei, such as α-particles, Oxygen and Iron nuclei, assuming different hadron interaction models. The computations are fulfilled with the CORSIKA 6.9 code using GHEISHA 2002, FLUKA 2011, UrQMD hadron generators for energy below 80 GeV/nucleon and QGSJET II for energy above 80 GeV/nucleon. The observed difference between hadron generators is widely discussed. The influence of different atmospheric parametrizations, namely US standard atmosphere, US standard atmosphere winter and summer profiles on ion production rate is studied. Assuming realistic primary cosmic ray mass composition, the ion production rate is obtained at several rigidity cut-offs - from 1 GV (high latitudes) to 15 GV (equatorial latitudes) using various hadron generators. The computations are compared with experimental data. A conclusion concerning the consistency of the hadron generators is stated.

Characterizations of atmospheric pressure low temperature plasma jets and their applications

NASA Astrophysics Data System (ADS)

Karakas, Erdinc

2011-12-01

Atmospheric pressure low temperature plasma jets (APLTPJs) driven by short pulses have recently received great attention because of their potential in biomedical and environmental applications. This potential is due to their user-friendly features, such as low temperature, low risk of arcing, operation at atmospheric pressure, easy handheld operation, and low concentration of ozone generation. Recent experimental observations indicate that an ionization wave exists and propagates along the plasma jet. The plasma jet created by this ionization wave is not a continuous medium but rather consists of a bullet-like-structure known as "Plasma Bullet". More interestingly, these plasma bullets actually have a donut-shaped makeup. The nature of the plasma bullet is especially interesting because it propagates in the ambient air at supersonic velocities without any externally applied electric field. In this dissertation, experimental insights are reported regarding the physical and chemical characteristics of the APLTPJs. The dynamics of the plasma bullet are investigated by means of a high-speed ICCD camera. A plasma bullet propagation model based on the streamer theory is confirmed with adequate explanations. It is also found that a secondary discharge, ignited by the charge accumulation on the dielectric electrode surfaces at the end of the applied voltage, interrupts the plasma bullet propagation due to an opposing current along the ionization channel. The reason for this interesting phenomenon is explained in detail. The plasma bullet comes to an end when the helium mole fraction along the ionization channel, or applied voltage, or both, are less than some critical values. The presence of an inert gas channel in the surrounding air, such as helium or argon, has a critical role in plasma bullet formation and propagation. For this reason, a fluid dynamics study is employed by a commercially available simulation software, COMSOL, based on finite element method. Spatio-temporally resolved optical emission spectroscopy (OES) gives the evolution of excited species along the trajectory of the plasma bullets. The APLTPJs' chemical composition includes short-lived species, such as He, N2, N+2 , and long-lived species, such as Hem (helium metastable), O3, NO, NO2. It is worth noting that metastable level excited atoms play an important role in promoting an enhanced chemistry along the plasma jet. Some of the APLTPJs' biomedical applications, such as dental hygiene applications and destruction of amyloid fibrils underlying Parkinson's disease, are explored along with an important discussion showing that the APLTPJs do not have a cytotoxic effect on living cells.

A novel APPI-MS setup for in situ degradation product studies of atmospherically relevant compounds: capillary atmospheric pressure photo ionization (cAPPI).

PubMed

Kersten, Hendrik; Derpmann, Valerie; Barnes, Ian; Brockmann, Klaus J; O'Brien, Rob; Benter, Thorsten

2011-11-01

We report on the development of a novel atmospheric pressure photoionization setup and its applicability for in situ degradation product studies of atmospherically relevant compounds. A custom miniature spark discharge lamp was embedded into an ion transfer capillary, which separates the atmospheric pressure from the low pressure region in the first differential pumping stage of a conventional atmospheric pressure ionization mass spectrometer. The lamp operates with a continuous argon flow and produces intense light emissions in the VUV. The custom lamp is operated windowless and efficiently illuminates the sample flow through the transfer capillary on an area smaller than 1 mm(2). Limits of detection in the lower ppbV range, a temporal resolution of milliseconds in the positive as well as the quasi simultaneously operating negative ion mode, and a significant reduction of ion transformation processes render this system applicable to real time studies of rapidly changing chemical systems. The method termed capillary atmospheric pressure photo ionization (cAPPI) is characterized with respect to the lamp emission properties as a function of the operating conditions, temporal response, and its applicability for in situ degradation product studies of atmospherically relevant compounds, respectively.

Control of the Earth's electric field intensity through solar wind modulation of galactic cosmic radiation: Support for a proposed atmospheric electrical sun-weather mechanism

NASA Technical Reports Server (NTRS)

Markson, R.

1980-01-01

The ionospheric potential and galactic cosmic radiation, found to be inversely correlated with the solar wind velocity are examined as being germane to weather modification. Since the ionospheric potential is proportional to the fair weather electric field intensity and cosmic radiation is the dominant source of atmospheric ionization, it is concluded that the Earth's overall electric field varies in phase with atmospheric ionization and that the latter is modulated by the solar wind. A proposed mechanism, in which solar control of ionizing radiation influences atmospheric electrification and thus possibly cloud physical processes is discussed. An experimental approach to critically test the proposed mechanism through comparison of the temporal variation of the Earth's electric field with conditions in the interplanetary medium is outlined.

Nanosecond repetitively pulsed discharges in air at atmospheric pressure—the spark regime

NASA Astrophysics Data System (ADS)

Pai, David Z.; Lacoste, Deanna A.; Laux, Christophe O.

2010-12-01

Nanosecond repetitively pulsed (NRP) spark discharges have been studied in atmospheric pressure air preheated to 1000 K. Measurements of spark initiation and stability, plasma dynamics, gas temperature and current-voltage characteristics of the spark regime are presented. Using 10 ns pulses applied repetitively at 30 kHz, we find that 2-400 pulses are required to initiate the spark, depending on the applied voltage. Furthermore, about 30-50 pulses are required for the spark discharge to reach steady state, following initiation. Based on space- and time-resolved optical emission spectroscopy, the spark discharge in steady state is found to ignite homogeneously in the discharge gap, without evidence of an initial streamer. Using measured emission from the N2 (C-B) 0-0 band, it is found that the gas temperature rises by several thousand Kelvin in the span of about 30 ns following the application of the high-voltage pulse. Current-voltage measurements show that up to 20-40 A of conduction current is generated, which corresponds to an electron number density of up to 1015 cm-3 towards the end of the high-voltage pulse. The discharge dynamics, gas temperature and electron number density are consistent with a streamer-less spark that develops homogeneously through avalanche ionization in volume. This occurs because the pre-ionization electron number density of about 1011 cm-3 produced by the high frequency train of pulses is above the critical density for streamer-less discharge development, which is shown to be about 108 cm-3.

Helium atmospheric pressure plasma jets touching dielectric and metal surfaces

NASA Astrophysics Data System (ADS)

Norberg, Seth A.; Johnsen, Eric; Kushner, Mark J.

2015-07-01

Atmospheric pressure plasma jets (APPJs) are being investigated in the context plasma medicine and biotechnology applications, and surface functionalization. The composition of the surface being treated ranges from plastics, liquids, and biological tissue, to metals. The dielectric constant of these materials ranges from as low as 1.5 for plastics to near 80 for liquids, and essentially infinite for metals. The electrical properties of the surface are not independent variables as the permittivity of the material being treated has an effect on the dynamics of the incident APPJ. In this paper, results are discussed from a computational investigation of the interaction of an APPJ incident onto materials of varying permittivity, and their impact on the discharge dynamics of the plasma jet. The computer model used in this investigation solves Poisson's equation, transport equations for charged and neutral species, the electron energy equation, and the Navier-Stokes equations for the neutral gas flow. The APPJ is sustained in He/O2 = 99.8/0.2 flowing into humid air, and is directed onto dielectric surfaces in contact with ground with dielectric constants ranging from 2 to 80, and a grounded metal surface. Low values of relative permittivity encourage propagation of the electric field into the treated material and formation and propagation of a surface ionization wave. High values of relative permittivity promote the restrike of the ionization wave and the formation of a conduction channel between the plasma discharge and the treated surface. The distribution of space charge surrounding the APPJ is discussed.

Global simulations of protoplanetary disks with net magnetic flux. I. Non-ideal MHD case

NASA Astrophysics Data System (ADS)

Béthune, William; Lesur, Geoffroy; Ferreira, Jonathan

2017-04-01

Context. The planet-forming region of protoplanetary disks is cold, dense, and therefore weakly ionized. For this reason, magnetohydrodynamic (MHD) turbulence is thought to be mostly absent, and another mechanism has to be found to explain gas accretion. It has been proposed that magnetized winds, launched from the ionized disk surface, could drive accretion in the presence of a large-scale magnetic field. Aims: The efficiency and the impact of these surface winds on the disk structure is still highly uncertain. We present the first global simulations of a weakly ionized disk that exhibits large-scale magnetized winds. We also study the impact of self-organization, which was previously demonstrated only in non-stratified models. Methods: We perform numerical simulations of stratified disks with the PLUTO code. We compute the ionization fraction dynamically, and account for all three non-ideal MHD effects: ohmic and ambipolar diffusions, and the Hall drift. Simplified heating and cooling due to non-thermal radiation is also taken into account in the disk atmosphere. Results: We find that disks can be accreting or not, depending on the configuration of the large-scale magnetic field. Magnetothermal winds, driven both by magnetic acceleration and heating of the atmosphere, are obtained in the accreting case. In some cases, these winds are asymmetric, ejecting predominantly on one side of the disk. The wind mass loss rate depends primarily on the average ratio of magnetic to thermal pressure in the disk midplane. The non-accreting case is characterized by a meridional circulation, with accretion layers at the disk surface and decretion in the midplane. Finally, we observe self-organization, resulting in axisymmetric rings of density and associated pressure "bumps". The underlying mechanism and its impact on observable structures are discussed.

Atmospheric Pressure-Thermal Desorption (AP-TD)/Electrospray Ionization-Mass Spectrometry for the Rapid Analysis of Bacillus Spores

USDA-ARS?s Scientific Manuscript database

A technique is described where an atmospheric pressure-thermal desorption (AP-TD) device and electrospray ionization (ESI)-mass spectrometry are coupled and used for the rapid analysis of Bacillus spores in complex matrices. The resulting AP-TD/ESI-MS technique combines the generation of volatile co...

Numerical calculation of cosmic ray ionization rate profiles in the middle atmosphere and lower ionosphere with relation to characteristic energy intervals

NASA Astrophysics Data System (ADS)

Velinov, Peter; Asenovski, Simeon; Mateev, Lachezar

2013-04-01

Numerical calculations of galactic cosmic ray (GCR) ionization rate profiles are presented for the middle atmosphere and lower ionosphere altitudes (35-90 km) for the full GCR composition (protons, alpha particles, and groups of heavier nuclei: light L, medium M, heavy H, very heavy VH). This investigation is based on a model developed by Velinov et al. (1974) and Velinov and Mateev (2008), which is further improved in the present paper. Analytical expressions for energy interval contributions are provided. An approximation of the ionization function on three energy intervals is used and for the first time the charge decrease interval for electron capturing (Dorman 2004) is investigated quantitatively. Development in this field of research is important for better understanding the impact of space weather on the atmosphere. GCRs influence the ionization and electric parameters in the atmosphere and also the chemical processes (ozone creation and depletion in the stratosphere) in it. The model results show good agreement with experimental data (Brasseur and Solomon 1986, Rosenberg and Lanzerotti 1979, Van Allen 1952).

Atmospheric helium and geomagnetic field reversals.

NASA Technical Reports Server (NTRS)

Sheldon, W. R.; Kern, J. W.

1972-01-01

The problem of the earth's helium budget is examined in the light of recent work on the interaction of the solar wind with nonmagnetic planets. It is proposed that the dominant mode of helium (He4) loss is ion pumping by the solar wind during geomagnetic field reversals, when the earth's magnetic field is very small. The interaction of the solar wind with the earth's upper atmosphere during such a period is found to involve the formation of a bow shock. The penetration altitude of the shock-heated solar plasma is calculated to be about 700 km, and ionization rates above this level are estimated for a cascade ionization (electron avalanche) process to average 10 to the 9th power ions/sq cm/sec. The calculated ionization rates and the capacity of the solar wind to remove ionized helium (He4) from the upper atmosphere during geomagnetic dipole reversals are sufficient to yield a secular equilibrium over geologic time scales. The upward transport of helium from the lower atmosphere under these conditions is found to be adequate to sustain the proposed loss rate.

Dynamics of the Mesopause Region as Revealed in Images of Polar Mesospheric Clouds

NASA Astrophysics Data System (ADS)

Bailey, Scott; Thurairajah, Brentha; Nielsen, Kim; Lumpe, Jerry; Randall, Cora; Taylor, Michael J.; Zhao, Yucheng

Studying the geospace response to variable inputs and waves from the lower atmosphere is particularly important since the induced variability competes with the solar and magnetic driving from above. Consequences for telecommunications, re-entry and satellite operations still need to be explored. The extent to which the effects of this quiescent atmospheric variability are transmitted to the magnetosphere is yet to be resolved. We thus stand right now at an exciting research frontier: understanding the cause-and-effect chain that connects tropospheric and strato-/mesospheric variability with geospace processes. CAWSES-II Task Group 4 (TG4) will therefore elucidate the dynamical coupling from the low and middle atmosphere to geospace including the upper atmosphere, ionosphere, and magnetosphere, for various frequencies and scales, such as gravity waves, tides, and planetary waves, and for equatorial, middle, and high latitudes. Attacking the problem clearly requires a systems approach involving experimentalists, data analysts and modelers from different communities. For that purpose, the most essential part of TG4 is to encourage interactions between atmospheric scientists and plasma scientists on all occasions. Four project are established in TG4, i.e., Project 1: How do atmospheric waves connect tropospheric weather with ITM variability?, Project 2: What is the relation between atmospheric waves and ionospheric instabilities?, Project 3: How do the different types of waves interact as they propagate through the stratosphere to the ionosphere?, and Project 4: How do thermospheric disturbances generated by auroral processes interact with the neutral and ionized atmosphere? A joint project with TG2 is also proposed for the topic of Project 5: How does climate change affects atmospheric waves in the ITM? In this presentation we show current status and future plan of CAWSES-II TG4 activities of 2009-2013.

Super-atmospheric pressure ionization mass spectrometry and its application to ultrafast online protein digestion analysis.

PubMed

Chen, Lee Chuin; Ninomiya, Satoshi; Hiraoka, Kenzo

2016-06-01

Ion source pressure plays a significant role in the process of ionization and the subsequent ion transmission inside a mass spectrometer. Pressurizing the ion source to a gas pressure greater than atmospheric pressure is a relatively new approach that aims to further improve the performance of atmospheric pressure ionization sources. For example, under a super-atmospheric pressure environment, a stable electrospray can be sustained for liquid with high surface tension such as pure water, because of the suppression of electric discharge. Even for nano-electrospray ionization (nano-ESI), which is known to work with aqueous solution, its stability and sensitivity can also be enhanced, particularly in the negative mode when the ion source is pressurized. A brief review on the development of super-atmospheric pressure ion sources, including high-pressure electrospray, field desorption and superheated ESI, and the strategies to interface these ion sources to a mass spectrometer will be given. Using a recent ESI prototype with an operating temperature at 220 °C under 27 atm, we also demonstrate that it is possible to achieve an online Asp-specific protein digestion analysis in which the whole processes of digestion, ionization and MS acquisition could be completed on the order of a few seconds. This method is fast, and the reaction can even be monitored on a near-real-time basis. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Effect of internal and external conditions on ionization processes in the FAPA ambient desorption/ionization source.

PubMed

Orejas, Jaime; Pfeuffer, Kevin P; Ray, Steven J; Pisonero, Jorge; Sanz-Medel, Alfredo; Hieftje, Gary M

2014-11-01

Ambient desorption/ionization (ADI) sources coupled to mass spectrometry (MS) offer outstanding analytical features: direct analysis of real samples without sample pretreatment, combined with the selectivity and sensitivity of MS. Since ADI sources typically work in the open atmosphere, ambient conditions can affect the desorption and ionization processes. Here, the effects of internal source parameters and ambient humidity on the ionization processes of the flowing atmospheric pressure afterglow (FAPA) source are investigated. The interaction of reagent ions with a range of analytes is studied in terms of sensitivity and based upon the processes that occur in the ionization reactions. The results show that internal parameters which lead to higher gas temperatures afforded higher sensitivities, although fragmentation is also affected. In the case of humidity, only extremely dry conditions led to higher sensitivities, while fragmentation remained unaffected.

Collison nebulizer as a new soft ionization source for mass spectrometry

NASA Astrophysics Data System (ADS)

Pervukhin, V. V.; Sheven', D. G.; Kolomiets, Yu. N.

2016-08-01

We have proposed that a Collison-type nebulizer be used as an ionization source for mass spectrometry with ionization under atmospheric pressure. This source does not require the use of electric voltage, radioactive sources, heaters, or liquid pumps. It has been shown that the number of ions produced by the 63Ni radioactive source is three to four times larger than the number of ions produced by acoustic ionization sources. We have considered the possibility of using a Collison-type nebulizer in combination with a vortex focusing system as an ion source for extractive ionization of compounds under atmospheric pressure. The ionization of volatile substances in crossflows of a charged aerosol and an analyte (for model compounds of the amine class, viz., diethylaniline, triamylamine, and cocaine) has been investigated. It has been shown that the limit of detecting cocaine vapor by this method is on the level of 4.6 × 10-14 g/cm3.

Ionization of NO at high temperature

NASA Technical Reports Server (NTRS)

Hansen, C. Frederick

1991-01-01

Space vehicles flying through the atmosphere at high speed are known to excite a complex set of chemical reactions in the atmospheric gases, ranging from simple vibrational excitation to dissociation, atom exchange, electronic excitation, ionization, and charge exchange. Simple arguments are developed for the temperature dependence of the reactions leading to ionization of NO, including the effect of vibrational electronic thermal nonequilibrium. NO ionization is the most important source of electrons at intermediate temperatures and at higher temperatures provides the trigger electrons that ionize atoms. Based on these arguments, recommendations are made for formulae which fit observed experimental results, and which include a dependence on both a heavy particle temperature and different vibration electron temperatures. In addition, these expressions will presumably provide the most reliable extrapolation of experimental results to much higher temperatures.

Atmospheric radiation flight dose rates

NASA Astrophysics Data System (ADS)

Tobiska, W. K.

2015-12-01

Space weather's effects upon the near-Earth environment are due to dynamic changes in the energy transfer processes from the Sun's photons, particles, and fields. Of the domains that are affected by space weather, the coupling between the solar and galactic high-energy particles, the magnetosphere, and atmospheric regions can significantly affect humans and our technology as a result of radiation exposure. Space Environment Technologies (SET) has been conducting space weather observations of the atmospheric radiation environment at aviation altitudes that will eventually be transitioned into air traffic management operations. The Automated Radiation Measurements for Aerospace Safety (ARMAS) system and Upper-atmospheric Space and Earth Weather eXperiment (USEWX) both are providing dose rate measurements. Both activities are under the ARMAS goal of providing the "weather" of the radiation environment to improve aircraft crew and passenger safety. Over 5-dozen ARMAS and USEWX flights have successfully demonstrated the operation of a micro dosimeter on commercial aviation altitude aircraft that captures the real-time radiation environment resulting from Galactic Cosmic Rays and Solar Energetic Particles. The real-time radiation exposure is computed as an effective dose rate (body-averaged over the radiative-sensitive organs and tissues in units of microsieverts per hour); total ionizing dose is captured on the aircraft, downlinked in real-time, processed on the ground into effective dose rates, compared with NASA's Langley Research Center (LaRC) most recent Nowcast of Atmospheric Ionizing Radiation System (NAIRAS) global radiation climatology model runs, and then made available to end users via the web and smart phone apps. Flight altitudes now exceed 60,000 ft. and extend above commercial aviation altitudes into the stratosphere. In this presentation we describe recent ARMAS and USEWX results.

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

NASA Technical Reports Server (NTRS)

Borsdorf, H.; Nazarov, E. G.; Eiceman, G. A.

2002-01-01

The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostly [M - 1]+ and [(M - 1)2H]+ ions while mainly [M - 3]+ and [(M - 3)H2O]+ ions were found for saturated cis/trans isomers using photoionization and 63Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63Ni ionization and photoionization. c. 2002 American Society for Mass Spectrometry.

Equatorial ion composition, 140-200 km, based on Atmosphere Explorer E data

NASA Technical Reports Server (NTRS)

Miller, N. J.; Grebowsky, J. M.; Hedin, A. E.; Spencer, N. W.

1993-01-01

We have used in situ measurements of ion composition and horizontal winds, taken from equatorial orbiting Atmosphere Explorer E in eccentric orbit during 1975-1976 to investigate the bottomside ionosphere at altitudes 140-200 km. Representative daytime altitude profiles of ionization were stable against wide variations in horizontal wind patterns. Special features that sometimes appeared in the structured nightside ionization were apparent ion composition waves, intermediate layers of enhanced ionization, and ionization depletions similar to equatorial ionization bubbles. Apparent ion composition waves displayed a horizontal wave length of about 650 km. Enhanced layers of ionization appeared to be newly separated from the bottomside midnight F layer; its ions were primarily NO(+) and O2(+) without significant densities of metallic ions, an indication that metallic ions are not required to produce the layers at altitudes above 140 km. Equatorial ionization depletions were observed at lower altitudes than previously reported and displayed molecular ion depletions as well as O(+) depletions.

An Open Port Sampling Interface for Liquid Introduction Atmospheric Pressure Ionization Mass Spectrometry

DOE PAGES

Van Berkel, Gary J.; Kertesz, Vilmos

2015-08-25

RATIONALE: A simple method to introduce unprocessed samples into a solvent for rapid characterization by liquid introduction atmospheric pressure ionization mass spectrometry has been lacking. The continuous flow, self-cleaning open port sampling interface introduced here fills this void. METHODS: The open port sampling interface used a vertically aligned, co-axial tube arrangement enabling solvent delivery to the sampling end of the device through the tubing annulus and solvent aspiration down the center tube and into the mass spectrometer ionization source via the commercial APCI emitter probe. The solvent delivery rate to the interface was set to exceed the aspiration rate creatingmore » a continuous sampling interface along with a constant, self-cleaning spillover of solvent from the top of the probe. RESULTS: Using the open port sampling interface with positive ion mode APCI and a hybrid quadrupole time of flight mass spectrometer, rapid, direct sampling and analysis possibilities are exemplified with plastics, ballpoint and felt tip ink pens, skin, and vegetable oils. These results demonstrated that the open port sampling interface could be used as a simple, versatile and self-cleaning system to rapidly introduce multiple types of unprocessed, sometimes highly concentrated and complex, samples into a solvent flow stream for subsequent ionization and analysis by mass spectrometry. The basic setup presented here could be incorporated with any self-aspirating liquid introduction ionization source (e.g., ESI, APCI, APPI, ICP, etc.) or any type of atmospheric pressure sampling ready mass spectrometer system. CONCLUSIONS: The open port sampling interface provides a means to introduce and quickly analyze unprocessed solid or liquid samples with liquid introduction atmospheric pressure ionization source without fear of sampling interface or ionization source contamination.« less

Selective ionization of dissolved organic nitrogen by positive ion atmospheric pressure photoionization coupled with Fourier transform ion cyclotron resonance mass spectrometry.

PubMed

Podgorski, David C; McKenna, Amy M; Rodgers, Ryan P; Marshall, Alan G; Cooper, William T

2012-06-05

Dissolved organic nitrogen (DON) comprises a heterogeneous family of organic compounds that includes both well-known biomolecules such as urea or amino acids and more complex, less characterized compounds such as humic and fulvic acids. Typically, DON represents only a small fraction of the total dissolved organic carbon pool and therefore presents inherent problems for chemical analysis and characterization. Here, we demonstrate that DON may be selectively ionized by atmospheric pressure photionization (APPI) and characterized at the molecular level by Fourier transform ion cyclotron resonance mass spectrometry. Unlike electrospray ionization (ESI), APPI ionizes polar and nonpolar compounds, and ionization efficiency is not determined by polarity. APPI is tolerant to salts, due to the thermal treatment inherent to nebulization, and thus avoids salt-adduct formation that can complicate ESI mass spectra. Here, for dissolved organic matter from various aquatic environments, we selectively ionize DON species that are not efficiently ionized by other ionization techniques and demonstrate significant signal-to-noise increase for nitrogen species by use of APPI relative to ESI.

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis.

PubMed

Nahan, Keaton S; Alvarez, Noe; Shanov, Vesselin; Vonderheide, Anne

2017-11-01

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R 2 ) of three target PAHs with phenanthrene internal standard. Graphical Abstract ᅟ.

Carbon Nanotube Fiber Ionization Mass Spectrometry: A Fundamental Study of a Multi-Walled Carbon Nanotube Functionalized Corona Discharge Pin for Polycyclic Aromatic Hydrocarbons Analysis

NASA Astrophysics Data System (ADS)

Nahan, Keaton S.; Alvarez, Noe; Shanov, Vesselin; Vonderheide, Anne

2017-09-01

Mass spectrometry continues to tackle many complicated tasks, and ongoing research seeks to simplify its instrumentation as well as sampling. The desorption electrospray ionization (DESI) source was the first ambient ionization source to function without extensive gas requirements and chromatography. Electrospray techniques generally have low efficiency for ionization of nonpolar analytes and some researchers have resorted to methods such as direct analysis in real time (DART) or desorption atmospheric pressure chemical ionization (DAPCI) for their analysis. In this work, a carbon nanotube fiber ionization (nanoCFI) source was developed and was found to be capable of solid phase microextraction (SPME) of nonpolar analytes as well as ionization and sampling similar to that of direct probe atmospheric pressure chemical ionization (DP-APCI). Conductivity and adsorption were maintained by utilizing a corona pin functionalized with a multi-walled carbon nanotube (MWCNT) thread. Quantitative work with the nanoCFI source with a designed corona discharge pin insert demonstrated linearity up to 0.97 (R2) of three target PAHs with phenanthrene internal standard. [Figure not available: see fulltext.

Atmospheric Pressure Ionization Permanent Magnet Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

PubMed Central

Vilkov, Andrey N.; Gamage, Chaminda M.; Misharin, Alexander S.; Doroshenko, Vladimir M.; Tolmachev, Dmitry A.; Tarasova, Irina A.; Kharybin, Oleg N.; Novoselov, Konstantin P.; Gorshkov, Michael V.

2007-01-01

A new Fourier Transform Ion Cyclotron Resonance mass spectrometer based on a permanent magnet with an atmospheric pressure ionization source was designed and constructed. A mass resolving power (full-width-at-half-maximum) of up to 80,000 in the electron ionization mode and 25,000 in the electrospray mode was obtained. Also, a mass measurement accuracy at low-ppm level has been demonstrated for peptide mixtures in a mass range of up to 1,200 m/z in the isotopically resolved mass spectra. PMID:17587594

Ionizing radiation in earth's atmosphere and in space near earth.

DOT National Transportation Integrated Search

2011-05-01

The Civil Aerospace Medical Institute of the FAA is charged with identifying health hazards in air travel and in : commercial human space travel. This report addresses one of these hazards ionizing radiation. : Ionizing radiation is a subatomic p...

Pyroelectricity Assisted Infrared-Laser Desorption Ionization (PAI-LDI) for Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Li, Yanyan; Ma, Xiaoxiao; Wei, Zhenwei; Gong, Xiaoyun; Yang, Chengdui; Zhang, Sichun; Zhang, Xinrong

2015-08-01

A new atmospheric pressure ionization method termed pyroelectricity-assisted infrared laser desorption ionization (PAI-LDI) was developed in this study. The pyroelectric material served as both sample target plate and enhancing ionization substrate, and an IR laser with wavelength of 1064 nm was employed to realize direct desorption and ionization of the analytes. The mass spectra of various compounds obtained on pyroelectric material were compared with those of other substrates. For the five standard substances tested in this work, LiNbO3 substrate produced the highest ion yield and the signal intensity was about 10 times higher than that when copper was used as substrate. For 1-adamantylamine, as low as 20 pg (132.2 fmol) was successfully detected. The active ingredient in (Compound Paracetamol and 1-Adamantylamine Hydrochloride Capsules), 1-adamantylamine, can be sensitively detected at an amount as low as 150 pg, when the medicine stock solution was diluted with urine. Monosaccharide and oligosaccharides in Allium Cepa L. juice was also successfully identified with PAI-LDI. The method did not require matrix-assisted external high voltage or other extra facility-assisted set-ups for desorption/ionization. This study suggested exciting application prospect of pyroelectric materials in matrix- and electricity-free atmospheric pressure mass spectrometry research.

Ionization enhancement in atmospheric pressure chemical ionization and suppression in electrospray ionization between target drugs and stable-isotope-labeled internal standards in quantitative liquid chromatography/tandem mass spectrometry.

PubMed

Liang, H R; Foltz, R L; Meng, M; Bennett, P

2003-01-01

The phenomena of ionization suppression in electrospray ionization (ESI) and enhancement in atmospheric pressure chemical ionization (APCI) were investigated in selected-ion monitoring and selected-reaction monitoring modes for nine drugs and their corresponding stable-isotope-labeled internal standards (IS). The results showed that all investigated target drugs and their co-eluting isotope-labeled IS suppress each other's ionization responses in ESI. The factors affecting the extent of suppression in ESI were investigated, including structures and concentrations of drugs, matrix effects, and flow rate. In contrast to the ESI results, APCI caused seven of the nine investigated target drugs and their co-eluting isotope-labeled IS to enhance each other's ionization responses. The mutual ionization suppression or enhancement between drugs and their isotope-labeled IS could possibly influence assay sensitivity, reproducibility, accuracy and linearity in quantitative liquid chromatography/mass spectrometry (LC/MS) and liquid chromatography/tandem mass spectrometry (LC/MS/MS). However, calibration curves were linear if an appropriate IS concentration was selected for a desired calibration range to keep the response factors constant. Copyright 2003 John Wiley & Sons, Ltd.

Meteoric Ions in Planetary Ionospheres

NASA Technical Reports Server (NTRS)

Pesnell, W. D.; Grebowsky, Joseph M.; Vondrak, Richard R. (Technical Monitor)

2001-01-01

Solar system debris, in the form of meteoroids, impacts every planet. The flux, relative composition and speed of the debris at each planet depends on the planet's size and location in the solar system. Ablation in the atmosphere evaporates the meteoric material and leaves behind metal atoms. During the ablation process metallic ions are formed by impact ionization. For small inner solar system planets, including Earth, this source of ionization is typically small compared to either photoionization or charge exchange with ambient molecular ions. For Earth, the atmosphere above the main deposition region absorbs the spectral lines capable of ionizing the major metallic atoms (Fe and Mg) so that charge exchange with ambient ions is the dominant source. Within the carbon dioxide atmosphere of Mars (and possibly Venus), photoionization is important in determining the ion density. For a heavy planet like Jupiter, far from the sun, impact ionization of ablated neutral atoms by impacts with molecules becomes a prominent source of ionization due to the gravitational acceleration to high incident speeds. We will describe the processes and location and extent of metal ion layers for Mars, Earth and Jupiter, concentrating on flagging the uncertainties in the models at the present time. This is an important problem, because low altitude ionosphere layers for the planets, particularly at night, probably consist predominantly of metallic ions. Comparisons with Earth will be used to illustrate the differing processes in the three planetary atmospheres.

Beyond Naphthenic Acids: Environmental Screening of Water from Natural Sources and the Athabasca Oil Sands Industry Using Atmospheric Pressure Photoionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry.

PubMed

Barrow, Mark P; Peru, Kerry M; Fahlman, Brian; Hewitt, L Mark; Frank, Richard A; Headley, John V

2015-09-01

There is a growing need for environmental screening of natural waters in the Athabasca region of Alberta, Canada, particularly in the differentiation between anthropogenic and naturally-derived organic compounds associated with weathered bitumen deposits. Previous research has focused primarily upon characterization of naphthenic acids in water samples by negative-ion electrospray ionization methods. Atmospheric pressure photoionization is a much less widely used ionization method, but one that affords the possibility of observing low polarity compounds that cannot be readily observed by electrospray ionization. This study describes the first usage of atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (in both positive-ion and negative-ion modes) to characterize and compare extracts of oil sands process water, river water, and groundwater samples from areas associated with oil sands mining activities. When comparing mass spectra previously obtained by electrospray ionization and data acquired by atmospheric pressure photoionization, there can be a doubling of the number of components detected. In addition to polar compounds that have previously been observed, low-polarity, sulfur-containing compounds and hydrocarbons that do not incorporate a heteroatom were detected. These latter components, which are not amenable to electrospray ionization, have potential for screening efforts within monitoring programs of the oil sands.

Ionospheric modification using relativistic electron beams

NASA Technical Reports Server (NTRS)

Banks, Peter M.; Fraser-Smith, Anthony C.; Gilchrist, B. E.

1990-01-01

The recent development of comparatively small electron linear accelerators (linacs) now makes possible a new class of ionospheric modification experiments using beams of relativistic electrons. These experiments can potentially provide much new information about the interactions of natural relativistic electrons with other particles in the upper atmosphere, and it may also make possible new forms of ionization structures extending down from the lower ionosphere into the largely un-ionized upper atmosphere. The consequences of firing a pulsed 1 A, 5 Mev electron beam downwards into the upper atmosphere are investigated. If a small pitch angle with respect to the ambient geomagnetic field is selected, the beam produces a narrow column of substantial ionization extending down from the source altitude to altitudes of approximately 40 to 45 km. This column is immediately polarized by the natural middle atmosphere fair weather electric field and an increasingly large potential difference is established between the column and the surrounding atmosphere. In the regions between 40 to 60 km, this potential can amount to many tens of kilovolts and the associated electric field can be greater than the field required for breakdown and discharge. Under these conditions, it may be possible to initiate lightning discharges along the initial ionization channel. Filamentation may also occur at the lower end to drive further currents in the partially ionized gases of the stratosphere. Such discharges would derive their energy from the earth-ionosphere electrical system and would be sustained until plasma depletion and/or electric field reduction brought the discharge under control. It is likely that this artificially-triggered lightning would produce measurable low-frequency radiation.

Dual parallel mass spectrometry for lipid and vitamin D analysis

USDA-ARS?s Scientific Manuscript database

There are numerous options for mass spectrometric analysis of lipids, including different types of ionization, and a wide variety of experiments using different scan modes that can be conducted. Atmospheric pressure chemical ionization (APCI) and electrospray ionization (ESI) provide complementary ...

Ground-Level Ozone Following Astrophysical Ionizing Radiation Events: An Additional Biological Hazard?

PubMed

Thomas, Brian C; Goracke, Byron D

2016-01-01

Astrophysical ionizing radiation events such as supernovae, gamma-ray bursts, and solar proton events have been recognized as a potential threat to life on Earth, primarily through depletion of stratospheric ozone and subsequent increase in solar UV radiation at Earth's surface and in the upper levels of the ocean. Other work has also considered the potential impact of nitric acid rainout, concluding that no significant threat is likely. Not yet studied to date is the potential impact of ozone produced in the lower atmosphere following an ionizing radiation event. Ozone is a known irritant to organisms on land and in water and therefore may be a significant additional hazard. Using previously completed atmospheric chemistry modeling, we examined the amount of ozone produced in the lower atmosphere for the case of a gamma-ray burst and found that the values are too small to pose a significant additional threat to the biosphere. These results may be extended to other ionizing radiation events, including supernovae and extreme solar proton events.

Bolt beam propagation analysis

NASA Astrophysics Data System (ADS)

Shokair, I. R.

BOLT (Beam on Laser Technology) is a rocket experiment to demonstrate electron beam propagation on a laser ionized plasma channel across the geomagnetic field in the ion focused regime (IFR). The beam parameters for BOLT are: beam current I(sub b) = 100 Amps, beam energy of 1--1.5 MeV (gamma =3-4), and a Gaussian beam and channel of radii r(sub b) = r(sub c) = 1.5 cm. The N+1 ionization scheme is used to ionize atomic oxygen in the upper atmosphere. This scheme utilizes 130 nm light plus three IR lasers to excite and then ionize atomic oxygen. The limiting factor for the channel strength is the energy of the 130 nm laser, which is assumed to be 1.6 mJ for BOLT. At a fixed laser energy and altitude (fixing the density of atomic oxygen), the range can be varied by adjusting the laser tuning, resulting in a neutralization fraction axial profile of the form: f(z) = f(sub 0) e(exp minus z)/R, where R is the range. In this paper we consider the propagation of the BOLT beam and calculate the range of the electron beam taking into account the fact that the erosion rates (magnetic and inductive) vary with beam length as the beam and channel dynamically respond to sausage and hose instabilities.

The isentropic exponent in plasmas

NASA Astrophysics Data System (ADS)

Burm, K. T. A. L.; Goedheer, W. J.; Schram, D. C.

1999-06-01

The isentropic exponent for gases is a physical quantity that can ease significantly the hydrodynamic modeling effort. In gas dynamics the isentropic exponent depends only on the number of degrees of freedom of the considered gas. The isentropic exponent for a plasma is lower due to an extra degree of freedom caused by ionization. In this paper it will be shown that, like for gases, the isentropic exponent for atomic plasmas is also constant, as long as the ionization degree is between 5%-80%. Only a very weak dependence on the electron temperature and the two nonequilibrium parameters remain. An argon plasma is used to demonstrate the behavior of the isentropic exponent on the plasma conditions, and to make an estimation of the value of the isentropic exponent of a customary plasma. For atmospheric plasmas, which usually have an electron temperature of about 1 eV, a sufficiently accurate estimate for the isentropic exponent of plasmas is 1.16.

Martian Ionospheric Observation and Modeling

NASA Astrophysics Data System (ADS)

González-Galindo, Francisco

2018-02-01

The Martian ionosphere is a plasma embedded within the neutral upper atmosphere of the planet. Its main source is the ionization of the CO2-dominated Martian mesosphere and thermosphere by the energetic EUV solar radiation. The ionosphere of Mars is subject to an important variability induced by changes in its forcing mechanisms (e.g., the UV solar flux) and by variations in the neutral atmosphere (e.g., the presence of global dust storms, atmospheric waves and tides, changes in atmospheric composition, etc.). Its vertical structure is dominated by a maximum in the electron concentration placed at about 120–140 km of altitude, coincident with the peak of the ionization rate. Below, a secondary peak produced by solar X-rays and photoelectron-impact ionization is observed. A sporadic third layer, possibly of meteoric origin, has been also detected below. The most abundant ion in the Martian ionosphere is O2+, although O+ can become more abundant in the upper ionospheric layers. While below about 180–200 km the Martian ionosphere is dominated by photochemical processes, above those altitudes the dynamics of the plasma become more important. The ionosphere is also an important source of escaping particles via processes such as dissociative recombination of ions or ion pickup. So, characterization of the ionosphere provides or can provide information about such disparate systems and processes as the solar radiation getting to the planet, the neutral atmosphere, the meteoric influx, the atmospheric escape to space, or the interaction of the planet with the solar wind. It is thus not surprising that the interest about this region dates from the beginning of the space era. From the first measurements provided by the Mariner 4 mission in the 1960s to the contemporaneous observations, still ongoing, by the Mars Express and MAVEN orbiters, our current knowledge of this atmospheric region is the consequence of the accumulation of more than 50 years of discontinuous measurements by different space missions. Numerical simulations by computational models able to simulate the processes that shape the ionosphere have also been commonly employed to obtain information about this region, to provide an interpretation of the observations and to fill their gaps. As a result, the Martian ionosphere is today the best known one after that of the Earth. However, there are still areas for which our knowledge is far from being complete. Examples are the details and balance of the mechanisms populating the nightside ionosphere, or a good understanding of the meteoric ionospheric layer and its variability.

An Integrated Modeling Study for Coordinated Observations of H, O, OH, and H2O(+) Emissions in the Coma and Ion Tail of the Comet Hale-Bopp

NASA Technical Reports Server (NTRS)

Smyth, William H.

2001-01-01

This project has two overall objectives. One objective is to advance our general understanding of both the comet neutral atmosphere and the cometary plasma in the atmosphere and ion tall. The other objective is to obtain specific key information about comet Hale-Bopp that is generally important for Hale-Bopp studies. The primary emphasis in this project is to analyze, in a self-consistent manner, excellent quality high resolution image and line profile observations obtained by the University of Wisconsin for H, O, OH, and H2O+ emissions from the inner coma, outer coma, and ion tail of Hale-Bopp. The information on the spatial and velocity distributions of H2O neutral and ionized photo-products in the inner coma, outer coma, and in the H2O+ ion tail is of substantial and direct importance in the development of an integrated understanding of the complex structure and dynamics of the neutral and plasma species in the atmosphere of Hale-Bopp in particular and comets in general. The H2O production rate of Hale-Bopp is determined and, together with the other information related to the structure and dynamics of the neutral and plasma atmospheres obtained in this study, provide critical information important for a wide variety of research conducted by other groups.

The Mega Mesospheric Parachute

NASA Technical Reports Server (NTRS)

Kloesel, Kurt J.; Oberto, Robert; Kinsey, Robert

2005-01-01

The current understanding and modeling of the upper reaches of the atmosphere is incomplete. Upper atmospheric interactions with the lower atmosphere, effects of ionizing radiation, high altitude cloud phenomena, and the dynamical interaction with the magnetosphere require greater definition. The scientific objective of obtaining a greater understanding of the upper atmosphere can be achieved by designing, implementing, testing, and utilizing a facility that provides long period in-situ measurements of the mesosphere. Current direct sub-sonic measurements of the upper atmosphere are hampered by the approximately one minute sub-sonic observation window of a ballistic sounding rocket regardless of the launch angle. In-situ measurements at greater than transonic speeds impart energy into the molecular atmospheric system and distort the true atmospheric chemistry. A long duration, sub-sonic capability will significantly enhance our ability to observe and measure: (1) mesospheric lightning phenomena (sprites and blue jets) (2) composition, structure and stratification of noctilucent clouds (3) physics of seasonal radar echoes, gravity wave phenomena (4) chemistry of mesospheric gaseous ratio mixing (5) mesospheric interaction of ionizing radiation (6) dynamic electric and magnetic fields This new facility will also provide local field measurements which complement those that can be obtained through external measurements from satellite and ground-based platforms. The 400 foot (approximately 130 meter) diameter lightweight mega-mesospheric parachute system, deployed with a sounding rocket, is proposed herein as a method to increase sub-sonic mesospheric measurement time periods by more than an order of magnitude. The report outlines a multi-year evolving science instrumentation suite in parallel with the development of the mega meso-chute facility. The developmental issues surrounding the meso-chute are chiefly materials selection (thermal and structural) and deployment mechanism physics. Three mission cases were conceived and developed to include cost and schedules estimates. Each scenario has increasing scientific utility with paralleling launch weight, parachute hang-time, deployment altitude, and parachute size: (1) Case #1: $8.4M@24 months, 6kg payload, 20 min., 50km alt., 80 m. dia. (2) Case #2: $10.4M@24 months, 6kg payload, 20 min., 60km alt, 130m. dia. (3) Case #3: $13.6M@36 months, 30kg payload, 30 min., 90km alt., 200m. dia. The initial breakout cost for the parachute system is approximately $2M@24 months. This report identifies that although the challenges of the mega-meso-chute may be difficult, they can be surmounted and valuable results can be achieved.

Laser-based methods for the analysis of low molecular weight compounds in biological matrices.

PubMed

Kiss, András; Hopfgartner, Gérard

2016-07-15

Laser-based desorption and/or ionization methods play an important role in the field of the analysis of low molecular-weight compounds (LMWCs) because they allow direct analysis with high-throughput capabilities. In the recent years there were several new improvements in ionization methods with the emergence of novel atmospheric ion sources such as laser ablation electrospray ionization or laser diode thermal desorption and atmospheric pressure chemical ionization and in sample preparation methods with the development of new matrix compounds for matrix-assisted laser desorption/ionization (MALDI). Also, the combination of ion mobility separation with laser-based ionization methods starts to gain popularity with access to commercial systems. These developments have been driven mainly by the emergence of new application fields such as MS imaging and non-chromatographic analytical approaches for quantification. This review aims to present these new developments in laser-based methods for the analysis of low-molecular weight compounds by MS and several potential applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Neutralization by a Corona Discharge Ionizer in Nitrogen Atmosphere

NASA Astrophysics Data System (ADS)

Ikeuchi, Toru; Takahashi, Kazunori; Ohkubo, Takahiro; Fujiwara, Tamiya

An electrostatic neutralization of multilayer-loading silicon wafers is demonstrated using a corona discharge ionizer in nitrogen atmosphere, where ac and dc voltages are applied to two needle electrodes for generation of the negative- and positive-charged particles, respectively. We observe a surface potential of the silicon wafer decreases from ±1kV to ±20V within three seconds. Moreover, the density profiles of the charged particles generated by the electrodes are experimentally and theoretically investigated in nitrogen and air atmospheres. Our results show the possibility that the negative-charged particles contributing to the electrostatic neutralization are electrons and negative ions in nitrogen and air atmospheres, respectively.

Space weather effects measured in atmospheric radiation on aircraft

NASA Astrophysics Data System (ADS)

Tobiska, W. K.; Bouwer, D.; Bailey, J. J.; Didkovsky, L. V.; Judge, K.; Wieman, S. R.; Atwell, W.; Gersey, B.; Wilkins, R.; Rice, D.; Schunk, R. W.; Bell, L. D.; Mertens, C. J.; Xu, X.; Wiltberger, M. J.; Wiley, S.; Teets, E.; Shea, M. A.; Smart, D. F.; Jones, J. B. L.; Crowley, G.; Azeem, S. I.; Halford, A. J.

2016-12-01

Space weather's effects upon the near-Earth environment are due to dynamic changes in the energy transfer processes from the Sun's photons, particles, and fields. Of the domains that are affected by space weather, the coupling between the solar and galactic high-energy particles, the magnetosphere, and atmospheric regions can significantly affect humans and our technology as a result of radiation exposure. Since 2013 Space Environment Technologies (SET) has been conducting observations of the atmospheric radiation environment at aviation altitudes using a small fleet of six instruments. The objective of this work is to improve radiation risk management in air traffic operations. Under the auspices of the Automated Radiation Measurements for Aerospace Safety (ARMAS) and Upper-atmospheric Space and Earth Weather eXperiment (USEWX) projects our team is making dose rate measurements on multiple aircraft flying global routes. Over 174 ARMAS and USEWX flights have successfully demonstrated the operation of a micro dosimeter on commercial aviation altitude aircraft that captures the radiation environment resulting from Galactic Cosmic Rays (GCRs), Solar Energetic Protons (SEPs), and outer radiation belt energetic electrons. The real-time radiation exposure is measured as an absorbed dose rate in silicon and then computed as an ambient dose equivalent rate for reporting dose relevant to radiative-sensitive organs and tissue in units of microsieverts per hour. ARMAS total ionizing absorbed dose is captured on the aircraft, downlinked in real-time, processed on the ground into ambient dose equivalent rates, compared with NASA's Langley Research Center (LaRC) most recent Nowcast of Atmospheric Ionizing Radiation System (NAIRAS) global radiation climatology model runs, and then made available to end users. Dose rates from flight altitudes up to 56,700 ft. are shown for flights across the planet under a variety of space weather conditions. We discuss several space weather effects on the atmospheric radiation environment, including the levels of GCR background radiation, small SEP events, and possible EMIC wave driven energetic electrons from the outer radiation belt creating "radiation" clouds in the troposphere.

Acetonitrile Ion Suppression in Atmospheric Pressure Ionization Mass Spectrometry

NASA Astrophysics Data System (ADS)

Colizza, Kevin; Mahoney, Keira E.; Yevdokimov, Alexander V.; Smith, James L.; Oxley, Jimmie C.

2016-11-01

Efforts to analyze trace levels of cyclic peroxides by liquid chromatography/mass spectrometry gave evidence that acetonitrile suppressed ion formation. Further investigations extended this discovery to ketones, linear peroxides, esters, and possibly many other types of compounds, including triazole and menadione. Direct ionization suppression caused by acetonitrile was observed for multiple adduct types in both electrospray ionization and atmospheric pressure chemical ionization. The addition of only 2% acetonitrile significantly decreased the sensitivity of analyte response. Efforts to identify the mechanism were made using various nitriles. The ion suppression was reduced by substitution of an acetonitrile hydrogen with an electron-withdrawing group, but was exacerbated by electron-donating or steric groups adjacent to the nitrile. Although current theory does not explain this phenomenon, we propose that polar interactions between the various functionalities and the nitrile may be forming neutral aggregates that manifest as ionization suppression.

Charge Assisted Laser Desorption/Ionization Mass Spectrometry of Droplets

PubMed Central

Jorabchi, Kaveh; Westphall, Michael S.; Smith, Lloyd M.

2008-01-01

We propose and evaluate a new mechanism to account for analyte ion signal enhancement in ultraviolet-laser desorption mass spectrometry of droplets in the presence of corona ions. Our new insights are based on timing control of corona ion production, laser desorption, and peptide ion extraction achieved by a novel pulsed corona apparatus. We demonstrate that droplet charging rather than gas-phase ion-neutral reactions is the major contributor to analyte ion generation from an electrically isolated droplet. Implications of the new mechanism, termed charge assisted laser desorption/ionization (CALDI), are discussed and contrasted to those of the laser desorption atmospheric pressure chemical ionization method (LD-APCI). It is also demonstrated that analyte ion generation in CALDI occurs with external electric fields about one order of magnitude lower than those needed for atmospheric pressure matrix assisted laser desorption/ionization or electrospray ionization of droplets. PMID:18387311

Portable Tandem Mass Spectrometer Analyzer

DTIC Science & Technology

1991-07-01

The planned instrument was to be small enough to be portable in small vehicles and was to be able to use either an atmospheric pressure ion source or a...conventional electron impact/chemical ionization ion source. In order to accomplish these developments an atmospheric pressure ionization source was...developed for a compact, commercially available tandem quadrupole mass spectrometer. This ion source could be readily exchanged with the conventional

From Dust to Dust: Protoplanetary Disk Accretion, Hot Jupiter Climates, and the Evaporation of Rocky Planets

NASA Astrophysics Data System (ADS)

Perez-Becker, Daniel Alonso

2013-12-01

This dissertation is composed of three independent projects in astrophysics concerning phenomena that are concurrent with the birth, life, and death of planets. In Chapters 1 & 2, we study surface layer accretion in protoplanetary disks driven stellar X-ray and far-ultraviolet (FUV) radiation. In Chapter 3, we identify the dynamical mechanisms that control atmospheric heat redistribution on hot Jupiters. Finally, in Chapter 4, we characterize the death of low-mass, short-period rocky planets by their evaporation into a dusty wind. Chapters 1 & 2: Whether protoplanetary disks accrete at observationally significant rates by the magnetorotational instability (MRI) depends on how well ionized they are. We find that disk surface layers ionized by stellar X-rays are susceptible to charge neutralization by condensates---ranging from mum-sized dust to angstrom-sized polycyclic aromatic hydrocarbons (PAHs). Ion densities in X-ray-irradiated surfaces are so low that ambipolar diffusion weakens the MRI. In contrast, ionization by stellar FUV radiation enables full-blown MRI turbulence in disk surface layers. Far-UV ionization of atomic carbon and sulfur produces a plasma so dense that it is immune to ion recombination on grains and PAHs. Even though the FUV-ionized layer is ˜10--100 times more turbulent than the X-ray-ionized layer, mass accretion rates of both layers are comparable because FUV photons penetrate to lower surface densities than do X-rays. We conclude that surface layer accretion occurs at observationally significant rates at radii ≳ 1--10 AU. At smaller radii, both X-ray- and FUV-ionized surface layers cannot sustain the accretion rates generated at larger distance and an additional means of transport is needed. In the case of transitional disks, it could be provided by planets. Chapter 3: Infrared light curves of transiting hot Jupiters present a trend in which the atmospheres of the hottest planets are less efficient at redistributing the stellar energy absorbed on their daysides than colder planets. Here we present a shallow water model of the atmospheric dynamics on synchronously rotating planets that explains why heat redistribution efficiency drops as stellar insolation rises. To interpret the model, we develop a scaling theory which shows that the timescale for gravity waves to propagate horizontally over planetary scales, tauwave, plays a dominant role in controlling the transition from small to large temperature contrasts. This implies that heat redistribution is governed by a wave-like process, similar to the one responsible for the weak temperature gradients in the Earth's tropics. When atmospheric drag can be neglected, the transition from small to large day-night temperature contrasts occurs when tauwave ˜ (taurad /o)1/2, where taurad is the radiative relaxation time of the atmosphere and o is the planetary rotation frequency. Our results subsume the more widely used timescale comparison for estimating heat redistribution efficiency between taurad and the horizontal day-night advection timescale, tauadv. Chapter 4: Short-period exoplanets can have dayside surface temperatures surpassing 2000 K, hot enough to vaporize rock and drive a thermal wind. Small enough planets evaporate completely. Here we construct a radiative-hydrodynamic model of atmospheric escape from strongly irradiated, low-mass rocky planets, accounting for dust-gas energy exchange in the wind. Rocky planets with masses ≲ 0.1 MEarth (less than twice the mass of Mercury) and surface temperatures ≳ 2000 K are found to disintegrate entirely in ≲ 10 Gyr. When our model is applied to Kepler planet candidate KIC 12557548b---which is believed to be a rocky body evaporating at a rate of dM/dt ≳ 0.1 MEarth/Gyr---our model yields a present-day planet mass of ≲ 0.02 MEarth or less than about twice the mass of the Moon. Mass loss rates depend so strongly on planet mass that bodies can reside on close-in orbits for Gyrs with initial masses comparable to or less than that of Mercury, before entering a final short-lived phase of catastrophic mass loss (which KIC 12557548b has entered). We estimate that for every object like KIC 12557548b, there should be 10--100 close-in quiescent progenitors with sub-day periods whose hard-surface transits may be detectable by Kepler---if the progenitors are as large as their maximal, Mercury-like sizes. KIC 12557548b may have lost ˜70% of its formation mass; today we may be observing its naked iron core.

Multiple parallel mass spectrometry for lipid and vitamin D analysis

USDA-ARS?s Scientific Manuscript database

Liquid chromatography (LC) coupled to mass spectrometry (MS) has become the method of choice for analysis of complex lipid samples. Two types of ionization sources have emerged as the most commonly used to couple LC to MS: atmospheric pressure chemical ionization (APCI) and electrospray ionization ...

Transmission geometry laserspray ionization vacuum using an atmospheric pressure inlet.

PubMed

Lutomski, Corinne A; El-Baba, Tarick J; Inutan, Ellen D; Manly, Cory D; Wager-Miller, James; Mackie, Ken; Trimpin, Sarah

2014-07-01

This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples.

Transmission Geometry Laserspray Ionization Vacuum Using an Atmospheric Pressure Inlet

PubMed Central

2015-01-01

This represents the first report of laserspray ionization vacuum (LSIV) with operation directly from atmospheric pressure for use in mass spectrometry. Two different types of electrospray ionization source inlets were converted to LSIV sources by equipping the entrance of the atmospheric pressure inlet aperture with a customized cone that is sealed with a removable glass plate holding the matrix/analyte sample. A laser aligned in transmission geometry (at 180° relative to the inlet) ablates the matrix/analyte sample deposited on the vacuum side of the glass slide. Laser ablation from vacuum requires lower inlet temperature relative to laser ablation at atmospheric pressure. However, higher inlet temperature is required for high-mass analytes, for example, α-chymotrypsinogen (25.6 kDa). Labile compounds such as gangliosides and cardiolipins are detected in the negative ion mode directly from mouse brain tissue as intact doubly deprotonated ions. Multiple charging enhances the ion mobility spectrometry separation of ions derived from complex tissue samples. PMID:24896880

Ultrapressure liquid chromatography-tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for quantification of 4-methoxydiphenylmethane in pharmacokinetic evaluation.

PubMed

Farhan, Nashid; Fitzpatrick, Sean; Shim, Yun M; Paige, Mikell; Chow, Diana Shu-Lian

2016-09-05

4-Methoxydiphenylmethane (4-MDM), a selective augmenter of Leukotriene A4 Hydrolase (LTA4H), is a new anti-inflammatory compound for potential treatment of chronic obstructive pulmonary disease (COPD). Currently, there is no liquid chromatography tandem mass spectrometric (LC-MS/MS) method for the quantification of 4-MDM. A major barrier for developing the LC-MS/MS method is the inability of electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI) to ionize 4-MDM due to its hydrophobicity and lack of any functional group for ionization. With the advent of atmospheric pressure photoionization (APPI) technique, many hydrophobic compounds have been demonstrated to ionize by charge transfer reactions. In this study, a highly sensitive ultrapressure liquid chromatography tandem mass spectrometry assay using atmospheric pressure photoionization (UPLC-APPI-MS/MS) for the quantifications of 4-MDM in rat plasma has been developed and validated. 4-MDM was extracted from the plasma by solid phase extraction (SPE) and separated chromatographically using a reverse phase C8 column. The photoionization (PI) was achieved by introducing anisole as a dopant to promote the reaction of charge transfer. The assay with a linear range of 5 (LLOQ)-400ngmL(-1) met the regulatory requirements for accuracy, precision and stability. The validated assay was employed to quantify the plasma concentrations of 4-MDM after an oral dosing in Sprague Dawley (SD) rats. Copyright © 2016 Elsevier B.V. All rights reserved.

Charge Exchange Reaction in Dopant-Assisted Atmospheric Pressure Chemical Ionization and Atmospheric Pressure Photoionization.

PubMed

Vaikkinen, Anu; Kauppila, Tiina J; Kostiainen, Risto

2016-08-01

The efficiencies of charge exchange reaction in dopant-assisted atmospheric pressure chemical ionization (DA-APCI) and dopant-assisted atmospheric pressure photoionization (DA-APPI) mass spectrometry (MS) were compared by flow injection analysis. Fourteen individual compounds and a commercial mixture of 16 polycyclic aromatic hydrocarbons were chosen as model analytes to cover a wide range of polarities, gas-phase ionization energies, and proton affinities. Chlorobenzene was used as the dopant, and methanol/water (80/20) as the solvent. In both techniques, analytes formed the same ions (radical cations, protonated molecules, and/or fragments). However, in DA-APCI, the relative efficiency of charge exchange versus proton transfer was lower than in DA-APPI. This is suggested to be because in DA-APCI both dopant and solvent clusters can be ionized, and the formed reagent ions can react with the analytes via competing charge exchange and proton transfer reactions. In DA-APPI, on the other hand, the main reagents are dopant-derived radical cations, which favor ionization of analytes via charge exchange. The efficiency of charge exchange in both DA-APPI and DA-APCI was shown to depend heavily on the solvent flow rate, with best efficiency seen at lowest flow rates studied (0.05 and 0.1 mL/min). Both DA-APCI and DA-APPI showed the radical cation of chlorobenzene at 0.05-0.1 mL/min flow rate, but at increasing flow rate, the abundance of chlorobenzene M(+.) decreased and reagent ion populations deriving from different gas-phase chemistry were recorded. The formation of these reagent ions explains the decreasing ionization efficiency and the differences in charge exchange between the techniques. Graphical Abstract ᅟ.

Dynamics of the High-latitude Ionospheric Irregularities During the 2015 St. Patrick's Day Storm

NASA Astrophysics Data System (ADS)

Cherniak, I.; Zakharenkova, I.; Redmon, R. J.; Andrzej, K.

2015-12-01

We presents results on the study of the high-latitude ionospheric irregularities observed in worldwide GPS data during the St. Patrick's Day geomagnetic storm (March 17, 2015). Multi-site GPS observations from more than 2500 ground-based GPS stations were used to analyze the dynamics of the ionospheric irregularities in the Northern and Southern Hemispheres. The most intense ionospheric irregularities lasted for more than 24 hours starting at 07 UT of March 17. This period correlates well with an increase of the auroral Hemispheric Power index. We find hemispheric asymmetries in the intensity and spatial structure of the ionospheric irregularities. Over North America the ionospheric irregularities zone expanded equatorward below ~45°N geographic latitude. Additionally, the strong mid and high latitude GPS phase irregularities in the auroral oval were found to be related to the formation of storm enhanced density, polar tongues of ionization and deepening of the main ionospheric trough through upper atmosphere ionization by energetic particle precipitations. Significant increases in the intensity of the irregularities within the polar cap region of both hemispheres were associated with the formation and evolution of the SED/TOI structures and polar patches.

A comparison between DART-MS and DSA-MS in the forensic analysis of writing inks.

PubMed

Drury, Nicholas; Ramotowski, Robert; Moini, Mehdi

2018-05-23

Ambient ionization mass spectrometry is gaining momentum in forensic science laboratories because of its high speed of analysis, minimal sample preparation, and information-rich results. One such application of ambient ionization methodology includes the analysis of writing inks from questioned documents where colorants of interest may not be soluble in common solvents, rendering thin layer chromatography (TLC) and separation-mass spectrometry methods such as LC/MS (-MS) impractical. Ambient ionization mass spectrometry uses a variety of ionization techniques such as penning ionization in Direct Analysis in Real Time (DART), and atmospheric pressure chemical ionization in Direct Sample Analysis (DSA), and electrospray ionization in Desorption Electrospray Ionization (DESI). In this manuscript, two of the commonly used ambient ionization techniques are compared: Perkin Elmer DSA-MS and IonSense DART in conjunction with a JEOL AccuTOF MS. Both technologies were equally successful in analyzing writing inks and produced similar spectra. DSA-MS produced less background signal likely because of its closed source configuration; however, the open source configuration of DART-MS provided more flexibility for sample positioning for optimum sensitivity and thereby allowing smaller piece of paper containing writing ink to be analyzed. Under these conditions, the minimum sample required for DART-MS was 1mm strokes of ink on paper, whereas DSA-MS required a minimum of 3mm. Moreover, both techniques showed comparable repeatability. Evaluation of the analytical figures of merit, including sensitivity, linear dynamic range, and repeatability, for DSA-MS and DART-MS analysis is provided. To the forensic context of the technique, DART-MS was applied to the analysis of United States Secret Service ink samples directly on a sampling mesh, and the results were compared with DSA-MS of the same inks on paper. Unlike analysis using separation mass spectrometry, which requires sample preparation, both DART-MS and DSA-MS successfully analyzed writing inks with minimal sample preparation. Copyright © 2018 Elsevier B.V. All rights reserved.

Atmospheric Ionizing Radiation and Human Exposure

NASA Technical Reports Server (NTRS)

Wilson, John W.; Mertens, Christopher J.; Goldhagen, Paul; Friedberg, W.; DeAngelis, G.; Clem, J. M.; Copeland, K.; Bidasaria, H. B.

2005-01-01

Atmospheric ionizing radiation is of interest, apart from its main concern of aircraft exposures, because it is a principal source of human exposure to radiations with high linear energy transfer (LET). The ionizing radiations of the lower atmosphere near the Earth s surface tend to be dominated by the terrestrial radioisotopes. especially along the coastal plain and interior low lands, and have only minor contributions from neutrons (11 percent). The world average is substantially larger but the high altitude cities especially have substantial contributions from neutrons (25 to 45 percent). Understanding the world distribution of neutron exposures requires an improved understanding of the latitudinal, longitudinal, altitude and spectral distribution that depends on local terrain and time. These issues are being investigated in a combined experimental and theoretical program. This paper will give an overview of human exposures and describe the development of improved environmental models.

Atmospheric Ionizing Radiation and Human Exposure

NASA Technical Reports Server (NTRS)

Wilson, J. W.; Goldhagen, P.; Friedberg, W.; DeAngelis, G.; Clem, J. M.; Copeland, K.; Bidasaria, H. B.

2004-01-01

Atmospheric ionizing radiation is of interest, apart from its main concern of aircraft exposures, because it is a principal source of human exposure to radiations with high linear energy transfer (LET). The ionizing radiations of the lower atmosphere near the Earth s surface tend to be dominated by the terrestrial radioisotopes especially along the coastal plain and interior low lands and have only minor contributions from neutrons (11 percent). The world average is substantially larger but the high altitude cities especially have substantial contributions from neutrons (25 to 45 percent). Understanding the world distribution of neutron exposures requires an improved understanding of the latitudinal, longitudinal, altitude and spectral distribution that depends on local terrain and time. These issues are being investigated in a combined experimental and theoretical program. This paper will give an overview of human exposures and describe the development of improved environmental models.

Increased ionization supports growth of aerosols into cloud condensation nuclei.

PubMed

Svensmark, H; Enghoff, M B; Shaviv, N J; Svensmark, J

2017-12-19

Ions produced by cosmic rays have been thought to influence aerosols and clouds. In this study, the effect of ionization on the growth of aerosols into cloud condensation nuclei is investigated theoretically and experimentally. We show that the mass-flux of small ions can constitute an important addition to the growth caused by condensation of neutral molecules. Under atmospheric conditions the growth from ions can constitute several percent of the neutral growth. We performed experimental studies which quantify the effect of ions on the growth of aerosols between nucleation and sizes >20 nm and find good agreement with theory. Ion-induced condensation should be of importance not just in Earth's present day atmosphere for the growth of aerosols into cloud condensation nuclei under pristine marine conditions, but also under elevated atmospheric ionization caused by increased supernova activity.

Hand-held portable desorption atmospheric pressure chemical ionization ion source for in situ analysis of nitroaromatic explosives.

PubMed

Jjunju, Fred P M; Maher, Simon; Li, Anyin; Syed, Sarfaraz U; Smith, Barry; Heeren, Ron M A; Taylor, Stephen; Cooks, R Graham

2015-10-06

A novel, lightweight (0.6 kg), solvent- and gas-cylinder-free, hand-held ion source based on desorption atmospheric pressure chemical ionization has been developed and deployed for the analysis of nitroaromatic explosives on surfaces in open air, offering portability for in-field analysis. A small, inexpensive, rechargeable lithium polymer battery was used to power the custom-designed circuitry within the device, which generates up to ±5 kV dc voltage to ignite a corona discharge plasma in air for up to 12 h of continuous operation, and allowing positive- and negative-ion mass spectrometry. The generated plasma is pneumatically transported to the surface to be interrogated by ambient air at a rate of 1-3.5 L/min, compressed using a small on-board diaphragm pump. The plasma source allows liquid or solid samples to be examined almost instantaneously without any sample preparation in the open environment. The advantages of low carrier gas and low power consumption (<6 W), as well as zero solvent usage, have aided in developing the field-ready, hand-held device for trigger-based, "near-real-time" sampling/ionization. Individual nitroaromatic explosives (such as 2,4,6-trinitrotoluene) can be easily detected in amounts as low as 5.8 pg with a linear dynamic range of at least 10 (10-100 pg), a relative standard deviation of ca. 7%, and an R(2) value of 0.9986. Direct detection of several nitroaromatic compounds in a complex mixture without prior sample preparation is demonstrated, and their identities are confirmed by tandem mass spectrometry fragmentation patterns.

Quantification of biogenic volatile organic compounds with a flame ionization detector using the effective carbon number concept

DOE PAGES

Faiola, C. L.; Erickson, M. H.; Fricaud, V. L.; ...

2012-08-10

Biogenic volatile organic compounds (BVOCs) are emitted into the atmosphere by plants and include isoprene, monoterpenes, sesquiterpenes, and their oxygenated derivatives. These BVOCs are among the principal factors influencing the oxidative capacity of the atmosphere in forested regions. BVOC emission rates are often measured by collecting samples onto adsorptive cartridges in the field and then transporting these samples to the laboratory for chromatographic analysis. One of the most commonly used detectors in chromatographic analysis is the flame ionization detector (FID). For quantitative analysis with an FID, relative response factors may be estimated using the effective carbon number (ECN) concept. Themore » purpose of this study was to determine the ECN for a variety of terpenoid compounds to enable improved quantification of BVOC measurements. A dynamic dilution system was developed to make quantitative gas standards of VOCs with mixing ratios from 20–55 ppb. For each experiment using this system, one terpene standard was co-injected with an internal reference, n-octane, and analyzed via an automated cryofocusing system interfaced to a gas chromatograph flame ionization detector and mass spectrometer (GC/MS/FID). The ECNs of 16 compounds (14 BVOCs) were evaluated with this approach, with each test compound analyzed at least three times. The difference between the actual carbon number and measured ECN ranged from -24% to -2%. Furthermore, the difference between theoretical ECN and measured ECN ranged from -22% to 9%. Measured ECN values were within 10% of theoretical ECN values for most terpenoid compounds.« less

Space Weather Nowcasting of Atmospheric Ionizing Radiation for Aviation Safety

NASA Technical Reports Server (NTRS)

Mertens, Christopher J.; Wilson, John W.; Blattnig, Steve R.; Solomon, Stan C.; Wiltberger, J.; Kunches, Joseph; Kress, Brian T.; Murray, John J.

2007-01-01

There is a growing concern for the health and safety of commercial aircrew and passengers due to their exposure to ionizing radiation with high linear energy transfer (LET), particularly at high latitudes. The International Commission of Radiobiological Protection (ICRP), the EPA, and the FAA consider the crews of commercial aircraft as radiation workers. During solar energetic particle (SEP) events, radiation exposure can exceed annual limits, and the number of serious health effects is expected to be quite high if precautions are not taken. There is a need for a capability to monitor the real-time, global background radiations levels, from galactic cosmic rays (GCR), at commercial airline altitudes and to provide analytical input for airline operations decisions for altering flight paths and altitudes for the mitigation and reduction of radiation exposure levels during a SEP event. The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) model is new initiative to provide a global, real-time radiation dosimetry package for archiving and assessing the biologically harmful radiation exposure levels at commercial airline altitudes. The NAIRAS model brings to bear the best available suite of Sun-Earth observations and models for simulating the atmospheric ionizing radiation environment. Observations are utilized from ground (neutron monitors), from the atmosphere (the METO analysis), and from space (NASA/ACE and NOAA/GOES). Atmospheric observations provide the overhead shielding information and the ground- and space-based observations provide boundary conditions on the GCR and SEP energy flux distributions for transport and dosimetry simulations. Dose rates are calculated using the parametric AIR (Atmospheric Ionizing Radiation) model and the physics-based HZETRN (High Charge and Energy Transport) code. Empirical models of the near-Earth radiation environment (GCR/SEP energy flux distributions and geomagnetic cut-off rigidity) are benchmarked against the physics-based CMIT (Coupled Magnetosphere- Ionosphere-Thermosphere) and SEP-trajectory models.

Clinical Application of Ambient Ionization Mass Spectrometry

PubMed Central

Li, Li-Hua; Hsieh, Hua-Yi; Hsu, Cheng-Chih

2017-01-01

Ambient ionization allows mass spectrometry analysis directly on the sample surface under atmospheric pressure with almost zero sample pretreatment. Since the development of desorption electrospray ionization (DESI) in 2004, many other ambient ionization techniques were developed. Due to their simplicity and low operation cost, rapid and on-site clinical mass spectrometry analysis becomes real. In this review, we will highlight some of the most widely used ambient ionization mass spectrometry approaches and their applications in clinical study. PMID:28337399

Magnetic Reconnection in Strongly Magnetized Regions of the Low Solar Chromosphere

NASA Astrophysics Data System (ADS)

Ni, Lei; Lukin, Vyacheslav S.; Murphy, Nicholas A.; Lin, Jun

2018-01-01

Magnetic reconnection in strongly magnetized regions around the temperature minimum region of the low solar atmosphere is studied by employing MHD-based simulations of a partially ionized plasma within a reactive 2.5D multi-fluid model. It is shown that in the absence of magnetic nulls in a low β plasma, the ionized and neutral fluid flows are well-coupled throughout the reconnection region. However, non-equilibrium ionization–recombination dynamics play a critical role in determining the structure of the reconnection region, leading to much lower temperature increases and a faster magnetic reconnection rate as compared to simulations that assume plasma to be in ionization–recombination equilibrium. The rate of ionization of the neutral component of the plasma is always faster than recombination within the current sheet region even when the initial plasma β is as high as {β }0=1.46. When the reconnecting magnetic field is in excess of a kilogauss and the plasma β is lower than 0.0145, the initially weakly ionized plasmas can become fully ionized within the reconnection region and the current sheet can be strongly heated to above 2.5× {10}4 K, even as most of the collisionally dissipated magnetic energy is radiated away. The Hall effect increases the reconnection rate slightly, but in the absence of magnetic nulls it does not result in significant asymmetries or change the characteristics of the reconnection current sheet down to meter scales.

Mass spectrometry imaging under ambient conditions.

PubMed

Wu, Chunping; Dill, Allison L; Eberlin, Livia S; Cooks, R Graham; Ifa, Demian R

2013-01-01

Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI for example the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information on the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue diagnostic purposes. Finally, we discuss the challenges in ambient MSI and include perspectives on the future of the field. Copyright © 2012 Wiley Periodicals, Inc.

Mass Spectrometry Imaging under Ambient Conditions

PubMed Central

Wu, Chunping; Dill, Allison L.; Eberlin, Livia S.; Cooks, R. Graham; Ifa, Demian R.

2012-01-01

Mass spectrometry imaging (MSI) has emerged as an important tool in the last decade and it is beginning to show potential to provide new information in many fields owing to its unique ability to acquire molecularly specific images and to provide multiplexed information, without the need for labeling or staining. In MSI, the chemical identity of molecules present on a surface is investigated as a function of spatial distribution. In addition to now standard methods involving MSI in vacuum, recently developed ambient ionization techniques allow MSI to be performed under atmospheric pressure on untreated samples outside the mass spectrometer. Here we review recent developments and applications of MSI emphasizing the ambient ionization techniques of desorption electrospray ionization (DESI), laser ablation electrospray ionization (LAESI), probe electrospray ionization (PESI), desorption atmospheric pressure photoionization (DAPPI), femtosecond laser desorption ionization (fs-LDI), laser electrospray mass spectrometry (LEMS), infrared laser ablation metastable-induced chemical ionization (IR-LAMICI), liquid microjunction surface sampling probe mass spectrometry (LMJ-SSP MS), nanospray desorption electrospray ionization (nano-DESI), and plasma sources such as the low temperature plasma (LTP) probe and laser ablation coupled to flowing atmospheric-pressure afterglow (LA-FAPA). Included are discussions of some of the features of ambient MSI including the ability to implement chemical reactions with the goal of providing high abundance ions characteristic of specific compounds of interest and the use of tandem mass spectrometry to either map the distribution of targeted molecules with high specificity or to provide additional MS information in the structural identification of compounds. We also describe the role of bioinformatics in acquiring and interpreting the chemical and spatial information obtained through MSI, especially in biological applications for tissue diagnostic purposes. Finally, we discuss the challenges in ambient MSI and include perspectives on the future of the field. PMID:22996621

Progress in Space Weather Modeling and Observations Needed to Improve the Operational NAIRAS Model Aircraft Radiation Exposure Predictions

NASA Astrophysics Data System (ADS)

Mertens, C. J.; Kress, B. T.; Wiltberger, M. J.; Tobiska, W.; Xu, X.

2011-12-01

The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) is a prototype operational model for predicting commercial aircraft radiation exposure from galactic and solar cosmic rays. NAIRAS predictions are currently streaming live from the project's public website, and the exposure rate nowcast is also available on the SpaceWx smartphone app for iPhone, IPad, and Android. Cosmic rays are the primary source of human exposure to high linear energy transfer radiation at aircraft altitudes, which increases the risk of cancer and other adverse health effects. Thus, the NAIRAS model addresses an important national need with broad societal, public health and economic benefits. The processes responsible for the variability in the solar wind, interplanetary magnetic field, solar energetic particle spectrum, and the dynamical response of the magnetosphere to these space environment inputs, strongly influence the composition and energy distribution of the atmospheric ionizing radiation field. During the development of the NAIRAS model, new science questions were identified that must be addressed in order to obtain a more reliable and robust operational model of atmospheric radiation exposure. Addressing these science questions require improvements in both space weather modeling and observations. The focus of this talk is to present these science questions, the proposed methodologies for addressing these science questions, and the anticipated improvements to the operational predictions of atmospheric radiation exposure. The overarching goal of this work is to provide a decision support tool for the aviation industry that will enable an optimal balance to be achieved between minimizing health risks to passengers and aircrew while simultaneously minimizing costs to the airline companies.

Real-Time Aircraft Cosmic Ray Radiation Exposure Predictions from the NAIRAS Model

NASA Astrophysics Data System (ADS)

Mertens, C. J.; Tobiska, W.; Kress, B. T.; Xu, X.

2012-12-01

The Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) is a prototype operational model for predicting commercial aircraft radiation exposure from galactic and solar cosmic rays. NAIRAS predictions are currently streaming live from the project's public website, and the exposure rate nowcast is also available on the SpaceWx smartphone app for iPhone, IPad, and Android. Cosmic rays are the primary source of human exposure to high linear energy transfer radiation at aircraft altitudes, which increases the risk of cancer and other adverse health effects. Thus, the NAIRAS model addresses an important national need with broad societal, public health and economic benefits. There is also interest in extending NAIRAS to the LEO environment to address radiation hazard issues for the emerging commercial spaceflight industry. The processes responsible for the variability in the solar wind, interplanetary magnetic field, solar energetic particle spectrum, and the dynamical response of the magnetosphere to these space environment inputs, strongly influence the composition and energy distribution of the atmospheric ionizing radiation field. Real-time observations are required at a variety of locations within the geospace environment. The NAIRAS model is driven by real-time input data from ground-, atmospheric-, and space-based platforms. During the development of the NAIRAS model, new science questions and observational data gaps were identified that must be addressed in order to obtain a more reliable and robust operational model of atmospheric radiation exposure. The focus of this talk is to present the current capabilities of the NAIRAS model, discuss future developments in aviation radiation modeling and instrumentation, and propose strategies and methodologies of bridging known gaps in current modeling and observational capabilities.

Characterization of non-polar aromatic hydrocarbons in crude oil using atmospheric pressure laser ionization and Fourier transform ion cyclotron resonance mass spectrometry (APLI FT-ICR MS).

PubMed

Schrader, Wolfgang; Panda, Saroj K; Brockmann, Klaus J; Benter, Thorsten

2008-07-01

We report on the successful application of the recently introduced atmospheric pressure laser ionization (APLI) method as a novel tool for the analysis of crude oil and its components. Using Fourier transform ion cyclotron resonance mass spectrometry, unambiguous determination of key compounds in this complex matrix with unprecedented sensitivity is presented.

The role of helium metastable states in radio-frequency driven helium-oxygen atmospheric pressure plasma jets: measurement and numerical simulation

NASA Astrophysics Data System (ADS)

Niemi, K.; Waskoenig, J.; Sadeghi, N.; Gans, T.; O'Connell, D.

2011-10-01

Absolute densities of metastable He(23S1) atoms were measured line-of-sight integrated along the discharge channel of a capacitively coupled radio-frequency driven atmospheric pressure plasma jet operated in technologically relevant helium-oxygen mixtures by tunable diode-laser absorption spectroscopy. The dependences of the He(23S1) density in the homogeneous-glow-like α-mode plasma with oxygen admixtures up to 1% were investigated. The results are compared with a one-dimensional numerical simulation, which includes a semi-kinetical treatment of the pronounced electron dynamics and the complex plasma chemistry (in total 20 species and 184 reactions). Very good agreement between measurement and simulation is found. The main formation mechanisms for metastable helium atoms are identified and analyzed, including their pronounced spatio-temporal dynamics. Penning ionization through helium metastables is found to be significant for plasma sustainment, while it is revealed that helium metastables are not an important energy carrying species into the jet effluent and therefore will not play a direct role in remote surface treatments.

Simple Ultraviolet Short-Pulse Intensity Diagnostic Method Using Atmosphere

NASA Astrophysics Data System (ADS)

Aota, Tatsuya; Takahashi, Eiichi; Losev, Leonid L.; Tabuchi, Takeyuki; Kato, Susumu; Matsumoto, Yuji; Okuda, Isao; Owadano, Yoshiro

2005-05-01

An ultraviolet (UV) short-pulse intensity diagnostic method using atmosphere as a nonlinear medium was developed. This diagnostic method is based on evaluating the ion charge of the two-photon ionization of atmospheric oxygen upon irradiation with a UV (238-299 nm) short-pulse laser. The observed ion signal increased proportionally to the input intensity to the power of ˜2.2, during the two-photon ionization of atmospheric oxygen. An autocorrelator was constructed and used to successfully measure a UV laser pulse of ˜400 fs duration. Since this diagnostic system is used in the open-air under windowless conditions, it can be set along the beam path and used as a UV intensity monitor.

Document authentication at molecular levels using desorption atmospheric pressure chemical ionization mass spectrometry imaging.

PubMed

Li, Ming; Jia, Bin; Ding, Liying; Hong, Feng; Ouyang, Yongzhong; Chen, Rui; Zhou, Shumin; Chen, Huanwen; Fang, Xiang

2013-09-01

Molecular images of documents were obtained by sequentially scanning the surface of the document using desorption atmospheric pressure chemical ionization mass spectrometry (DAPCI-MS), which was operated in either a gasless, solvent-free or methanol vapor-assisted mode. The decay process of the ink used for handwriting was monitored by following the signal intensities recorded by DAPCI-MS. Handwritings made using four types of inks on four kinds of paper surfaces were tested. By studying the dynamic decay of the inks, DAPCI-MS imaging differentiated a 10-min old from two 4 h old samples. Non-destructive forensic analysis of forged signatures either handwritten or computer-assisted was achieved according to the difference of the contour in DAPCI images, which was attributed to the strength personalized by different writers. Distinction of the order of writing/stamping on documents and detection of illegal printings were accomplished with a spatial resolution of about 140 µm. A Matlab® written program was developed to facilitate the visualization of the similarity between signature images obtained by DAPCI-MS. The experimental results show that DAPCI-MS imaging provides rich information at the molecular level and thus can be used for the reliable document analysis in forensic applications. © 2013 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons, Ltd.

A review of shock waves around aeroassisted orbital transfer vehicles

NASA Technical Reports Server (NTRS)

Park, C.

1986-01-01

Aeroassisted orbital transfer vehicles (AOTVs) are a proposed type of reusable spacecraft that would be used to transport cargoes from one earth-bound orbit to another. Such vehicles could be based on the proposed space station and used to transport commercial satellites from the space station to geostationary orbits or to polar orbits and return. During a mission, AOTVs would fly through earth's atmosphere, thus generating aerodynamic forces that could be used for decelerating the vehicles or changing their direction. AOTV research findings were concerned with the shock-wave-induced, high-temperature airflows that would be produced around these vehicles during atmospheric flight. Special emphasis was placed on the problems of: (1) the chemical physics of multitemperature, ionizing, nonequilibrium air flows, and (2) the dynamics of the flows in the base region of a blunt body with complex afterbody geometry.

A review of shock waves around aeroassisted orbital transfer vehicles

NASA Technical Reports Server (NTRS)

Park, C.

1985-01-01

Aeroassisted orbital transfer vehicles (AOTVs) are a proposed type of reusable spacecraft that would be used to transport cargoes from one Earth-bound orbit to another. Such vehicles could be based on the proposed space station and used to transport commercial satellites from the space station to geostationary orbits or to polar orbits and return. During a mission, AOTVs would fly through Earth's atmosphere, thus generating aerodynamic forces that could be used for decelerating the vehicles or changing their direction. AOTV research findings were concerned with the shock-wave-induced, high-temperature airflows that would be produced around these vehicles during atmospheric flight. Special emphasis was placed on the problems of: (1) the chemical physics of multitemperature, ionizing, nonequilibrium air flows, and (2) the dynamics of the flows in the base region of a blunt body with complex afterbody geometry.

Microplasma discharge vacuum ultraviolet photoionization source for atmospheric pressure ionization mass spectrometry.

PubMed

Symonds, Joshua M; Gann, Reuben N; Fernández, Facundo M; Orlando, Thomas M

2014-09-01

In this paper, we demonstrate the first use of an atmospheric pressure microplasma-based vacuum ultraviolet (VUV) photoionization source in atmospheric pressure mass spectrometry applications. The device is a robust, easy-to-operate microhollow cathode discharge (MHCD) that enables generation of VUV photons from Ne and Ne/H(2) gas mixtures. Photons were detected by excitation of a microchannel plate detector and by analysis of diagnostic sample ions using a mass spectrometer. Reactive ions, charged particles, and metastables produced in the discharge were blocked from entering the ionization region by means of a lithium fluoride window, and photoionization was performed in a nitrogen-purged environment. By reducing the output pressure of the MHCD, we observed heightened production of higher-energy photons, making the photoionization source more effective. The initial performance of the MHCD VUV source has been evaluated by ionizing model analytes such as acetone, azulene, benzene, dimethylaniline, and glycine, which were introduced in solid or liquid phase. These molecules represent species with both high and low proton affinities, and ionization energies ranging from 7.12 to 9.7 eV.

Ion-Neutral Coupling in Solar Prominence

NASA Technical Reports Server (NTRS)

Gilbert, H.; DeVore, C. R.; Karpen, J.; Kucera, T.; Antiochos, S.; Kawashima, R.

2011-01-01

Coupling between ions and neutrals in magnetized plasmas is fundamentally important to many aspects of heliophysics, including our ionosphere, the solar chromosphere, the solar wind interaction with planetary atmospheres, and the interface between the heliosphere and the interstellar medium. Ion-neutral coupling also plays a major role in the physics of solar prominences. By combining theory, modeling, and observations we are working toward a better understanding of the structure and dynamics of partially ionized prominence plasma. Two key questions are addressed in the present work: 1) what physical mechanism(s) sets the cross-field scale of prominence threads? 2) Are ion-neutral interactions responsible for the vertical flows and structure in prominences? We present initial results from a study investigating what role ion-neutral interactions play in prominence dynamics and structure. This research was supported by NASA.

Comparison of Atmospheric Pressure Chemical Ionization and Field Ionization Mass Spectrometry for the Analysis of Large Saturated Hydrocarbons.

PubMed

Jin, Chunfen; Viidanoja, Jyrki; Li, Mingzhe; Zhang, Yuyang; Ikonen, Elias; Root, Andrew; Romanczyk, Mark; Manheim, Jeremy; Dziekonski, Eric; Kenttämaa, Hilkka I

2016-11-01

Direct infusion atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was compared to field ionization mass spectrometry (FI-MS) for the determination of hydrocarbon class distributions in lubricant base oils. When positive ion mode APCI with oxygen as the ion source gas was employed to ionize saturated hydrocarbon model compounds (M) in hexane, only stable [M - H] + ions were produced. Ion-molecule reaction studies performed in a linear quadrupole ion trap suggested that fragment ions of ionized hexane can ionize saturated hydrocarbons via hydride abstraction with minimal fragmentation. Hence, APCI-MS shows potential as an alternative of FI-MS in lubricant base oil analysis. Indeed, the APCI-MS method gave similar average molecular weights and hydrocarbon class distributions as FI-MS for three lubricant base oils. However, the reproducibility of APCI-MS method was found to be substantially better than for FI-MS. The paraffinic content determined using the APCI-MS and FI-MS methods for the base oils was similar. The average number of carbons in paraffinic chains followed the same increasing trend from low viscosity to high viscosity base oils for the two methods.

Partially Ionized Plasmas in Astrophysics

NASA Astrophysics Data System (ADS)

Ballester, José Luis; Alexeev, Igor; Collados, Manuel; Downes, Turlough; Pfaff, Robert F.; Gilbert, Holly; Khodachenko, Maxim; Khomenko, Elena; Shaikhislamov, Ildar F.; Soler, Roberto; Vázquez-Semadeni, Enrique; Zaqarashvili, Teimuraz

2018-03-01

Partially ionized plasmas are found across the Universe in many different astrophysical environments. They constitute an essential ingredient of the solar atmosphere, molecular clouds, planetary ionospheres and protoplanetary disks, among other environments, and display a richness of physical effects which are not present in fully ionized plasmas. This review provides an overview of the physics of partially ionized plasmas, including recent advances in different astrophysical areas in which partial ionization plays a fundamental role. We outline outstanding observational and theoretical questions and discuss possible directions for future progress.

Low latitude middle atmosphere ionization studies

NASA Technical Reports Server (NTRS)

Bassi, J. P.

1976-01-01

Low latitude middle atmosphere ionization was studied with data obtained from three blunt conductivity probes and one Gerdien condenser. An investigation was conducted into the effects of various ionization sources in the 40 to 65 Km altitude range. An observed enhancement of positive ion conductivity taking place during the night can be explained by an atmsopheric effect, with cosmic rays being the only source of ionization only if the ion-ion recombination coefficient (alpha sub i) is small(10 to the -7 power cu cm/s) and varies greatly with altitude. More generally accepted values of alpha sub i ( approximately equal to 3x10 to the -7 power cu cm/s) require an additional source of ionization peaking at about 65 Km, and corresponding approximately to the integrated effect of an X-ray flux measured on a rocket flown in conjunction with the ionization measurements. The reasonable assumption of an alpha sub i which does not vary with altitude in the 50-70 Km range implies an even greater value alpha sub i and a more intense and harder X-ray spectrum.

The Upper Atmosphere; Threshold of Space.

ERIC Educational Resources Information Center

Bird, John

This booklet contains illustrations of the upper atmosphere, describes some recent discoveries, and suggests future research questions. It contains many color photographs. Sections include: (1) "Where Does Space Begin?"; (2) "Importance of the Upper Atmosphere" (including neutral atmosphere, ionized regions, and balloon and investigations); (3)…

Radiation-Related Risk Analysis for Atmospheric Flight Civil Aviation Flight Personnel

NASA Technical Reports Server (NTRS)

DeAngelis, G.; Wilson, J. W.

2003-01-01

Human data on low dose rate radiation exposure and consequent effects are not readily available, and this fact generates groundtruth concerns for all risk assessment techniques for possible health effects induced by the space radiation environment, especially for long term missions like those foreseen now and in the near future. A large amount of such data may be obtained through civil aviation flight personnel cohorts, in the form of epidemiological studies on delayed health effects induced by the cosmic-ray generated atmospheric radiation environment, a high- LET low dose and low dose rate ionizing radiation with its typical neutron component, to which flight personnel are exposed all throughout their work activity. In the perspective of worldwide studies on radiation exposure of the civil aviation flight personnel, all the available results from previous studies on flight personnel radiation exposure have been examined in various ways (i.e. literature review, meta-analysis) to evaluate possible significant associations between atmospheric ionizing radiation environment and health risks, and to assess directions for future investigations. The physical characteristics of the atmospheric ionizing radiation environment make the results obtained for atmospheric flight personnel relevant for space exploration.

Martian Dust Devil Electron Avalanche Process and Associated Electrochemistry

NASA Technical Reports Server (NTRS)

Jackson, Telana L.; Farrell, William M.; Delory, Gregory T.; Nithianandam, Jeyasingh

2010-01-01

Mars' dynamic atmosphere displays localized dust devils and larger, global dust storms. Based on terrestrial analog studies, electrostatic modeling, and laboratory work these features will contain large electrostatic fields formed via triboelectric processes. In the low-pressure Martian atmosphere, these fields may create an electron avalanche and collisional plasma due to an increase in electron density driven by the internal electrical forces. To test the hypothesis that an electron avalanche is sustained under these conditions, a self-consistent atmospheric process model is created including electron impact ionization sources and electron losses via dust absorption, electron dissociation attachment, and electron/ion recombination. This new model is called the Dust Devil Electron Avalanche Model (DDEAM). This model solves simultaneously nine continuity equations describing the evolution of the primary gaseous chemical species involved in the electrochemistry. DDEAM monitors the evolution of the electrons and primary gas constituents, including electron/water interactions. We especially focus on electron dynamics and follow the electrons as they evolve in the E field driven collisional gas. When sources and losses are self-consistently included in the electron continuity equation, the electron density grows exponentially with increasing electric field, reaching an equilibrium that forms a sustained time-stable collisional plasma. However, the character of this plasma differs depending upon the assumed growth rate saturation process (chemical saturation versus space charge). DDEAM also shows the possibility of the loss of atmospheric methane as a function of electric field due to electron dissociative attachment of the hydrocarbon. The methane destruction rates are presented and can be included in other larger atmospheric models.

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source

NASA Astrophysics Data System (ADS)

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H]+ was observed in the case of individual alkanes (C5-C19) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. [Figure not available: see fulltext.

Investigation and Applications of In-Source Oxidation in Liquid Sampling-Atmospheric Pressure Afterglow Microplasma Ionization (LS-APAG) Source.

PubMed

Xie, Xiaobo; Wang, Zhenpeng; Li, Yafeng; Zhan, Lingpeng; Nie, Zongxiu

2017-06-01

A liquid sampling-atmospheric pressure afterglow microplasma ionization (LS-APAG) source is presented for the first time, which is embedded with both electrospray ionization (ESI) and atmospheric pressure afterglow microplasma ionization (APAG) techniques. This ion source is capable of analyzing compounds with diverse molecule weights and polarities. An unseparated mixture sample was detected as a proof-of-concept, giving complementary information (both polarities and non-polarities) with the two ionization modes. It should also be noted that molecular mass can be quickly identified by ESI with clean and simple spectra, while the structure can be directly studied using APAG with in-source oxidation. The ionization/oxidation mechanism and applications of the LS-APAG source have been further explored in the analysis of nonpolar alkanes and unsaturated fatty acids/esters. A unique [M + O - 3H] + was observed in the case of individual alkanes (C 5 -C 19 ) and complex hydrocarbons mixture under optimized conditions. Moreover, branched alkanes generated significant in-source fragments, which could be further applied to the discrimination of isomeric alkanes. The technique also facilitates facile determination of double bond positions in unsaturated fatty acids/esters due to diagnostic fragments (the acid/ester-containing aldehyde and acid oxidation products) generated by on-line ozonolysis in APAG mode. Finally, some examples of in situ APAG analysis by gas sampling and surface sampling were given as well. Graphical Abstract ᅟ.

Comparison of direct and alternating current vacuum ultraviolet lamps in atmospheric pressure photoionization.

PubMed

Vaikkinen, Anu; Haapala, Markus; Kersten, Hendrik; Benter, Thorsten; Kostiainen, Risto; Kauppila, Tiina J

2012-02-07

A direct current induced vacuum ultraviolet (dc-VUV) krypton discharge lamp and an alternating current, radio frequency (rf) induced VUV lamp that are essentially similar to lamps in commercial atmospheric pressure photoionization (APPI) ion sources were compared. The emission distributions along the diameter of the lamp exit window were measured, and they showed that the beam of the rf lamp is much wider than that of the dc lamp. Thus, the rf lamp has larger efficient ionization area, and it also emits more photons than the dc lamp. The ionization efficiencies of the lamps were compared using identical spray geometries with both lamps in microchip APPI mass spectrometry (μAPPI-MS) and desorption atmospheric pressure photoionization-mass spectrometry (DAPPI-MS). A comprehensive view on the ionization was gained by studying six different μAPPI solvent compositions, five DAPPI spray solvents, and completely solvent-free DAPPI. The observed reactant ions for each solvent composition were very similar with both lamps except for toluene, which showed a higher amount of solvent originating oxidation products with the rf lamp than with the dc lamp in μAPPI. Moreover, the same analyte ions were detected with both lamps, and thus, the ionization mechanisms with both lamps are similar. The rf lamp showed a higher ionization efficiency than the dc lamp in all experiments. The difference between the lamp ionization efficiencies was greatest when high ionization energy (IE) solvent compositions (IEs above 10 eV), i.e., hexane, methanol, and methanol/water, (1:1 v:v) were used. The higher ionization efficiency of the rf lamp is likely due to the larger area of high intensity light emission, and the resulting larger efficient ionization area and higher amount of photons emitted. These result in higher solvent reactant ion production, which in turn enables more efficient analyte ion production. © 2012 American Chemical Society

INVESTIGATION OF THE HUMIDITY EFFECT ON THE FAC-IR-300 IONIZATION CHAMBER RESPONSE.

PubMed

Mohammadi, Seyed Mostafa; Tavakoli-Anbaran, Hossein

2018-02-01

The free-air ionization chamber is communicating with the ambient air, therefore, the atmospheric parameters such as temperature, pressure and humidity effect on the ionization chamber performance. The free-air ionization chamber, entitled as FAC-IR-300, that design at the Atomic Energy Organization of Iran, AEOI, is required the atmospheric correction factors for correct the chamber reading. In this article, the effect of humidity on the ionization chamber response was investigated. For this reason, was introduced the humidity correction factor, kh. In this article, the Monte Carlo simulation was used to determine the kh factor. The simulation results show in relative humidities between 30% to 80%, the kh factor is equal 0.9970 at 20°C and 0.9975 at 22°C. From the simulation results, at low energy the energy dependence of the kh factor is significant and with increasing energy this dependence is negligible. © The Author 2017. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory.

PubMed

Sissay, Adonay; Abanador, Paul; Mauger, François; Gaarde, Mette; Schafer, Kenneth J; Lopata, Kenneth

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagating the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sissay, Adonay; Abanador, Paul; Mauger, François

2016-09-07

Strong-field ionization and the resulting electronic dynamics are important for a range of processes such as high harmonic generation, photodamage, charge resonance enhanced ionization, and ionization-triggered charge migration. Modeling ionization dynamics in molecular systems from first-principles can be challenging due to the large spatial extent of the wavefunction which stresses the accuracy of basis sets, and the intense fields which require non-perturbative time-dependent electronic structure methods. In this paper, we develop a time-dependent density functional theory approach which uses a Gaussian-type orbital (GTO) basis set to capture strong-field ionization rates and dynamics in atoms and small molecules. This involves propagatingmore » the electronic density matrix in time with a time-dependent laser potential and a spatial non-Hermitian complex absorbing potential which is projected onto an atom-centered basis set to remove ionized charge from the simulation. For the density functional theory (DFT) functional we use a tuned range-separated functional LC-PBE*, which has the correct asymptotic 1/r form of the potential and a reduced delocalization error compared to traditional DFT functionals. Ionization rates are computed for hydrogen, molecular nitrogen, and iodoacetylene under various field frequencies, intensities, and polarizations (angle-dependent ionization), and the results are shown to quantitatively agree with time-dependent Schrödinger equation and strong-field approximation calculations. This tuned DFT with GTO method opens the door to predictive all-electron time-dependent density functional theory simulations of ionization and ionization-triggered dynamics in molecular systems using tuned range-separated hybrid functionals.« less

Solar flare model atmospheres

NASA Technical Reports Server (NTRS)

Hawley, Suzanne L.; Fisher, George H.

1993-01-01

Solar flare model atmospheres computed under the assumption of energetic equilibrium in the chromosphere are presented. The models use a static, one-dimensional plane parallel geometry and are designed within a physically self-consistent coronal loop. Assumed flare heating mechanisms include collisions from a flux of non-thermal electrons and x-ray heating of the chromosphere by the corona. The heating by energetic electrons accounts explicitly for variations of the ionized fraction with depth in the atmosphere. X-ray heating of the chromosphere by the corona incorporates a flare loop geometry by approximating distant portions of the loop with a series of point sources, while treating the loop leg closest to the chromospheric footpoint in the plane-parallel approximation. Coronal flare heating leads to increased heat conduction, chromospheric evaporation and subsequent changes in coronal pressure; these effects are included self-consistently in the models. Cooling in the chromosphere is computed in detail for the important optically thick HI, CaII and MgII transitions using the non-LTE prescription in the program MULTI. Hydrogen ionization rates from x-ray photo-ionization and collisional ionization by non-thermal electrons are included explicitly in the rate equations. The models are computed in the 'impulsive' and 'equilibrium' limits, and in a set of intermediate 'evolving' states. The impulsive atmospheres have the density distribution frozen in pre-flare configuration, while the equilibrium models assume the entire atmosphere is in hydrostatic and energetic equilibrium. The evolving atmospheres represent intermediate stages where hydrostatic equilibrium has been established in the chromosphere and corona, but the corona is not yet in energetic equilibrium with the flare heating source. Thus, for example, chromospheric evaporation is still in the process of occurring.

Electron-impact-ionization dynamics of S F6

NASA Astrophysics Data System (ADS)

Bull, James N.; Lee, Jason W. L.; Vallance, Claire

2017-10-01

A detailed understanding of the dissociative electron ionization dynamics of S F6 is important in the modeling and tuning of dry-etching plasmas used in the semiconductor manufacture industry. This paper reports a crossed-beam electron ionization velocity-map imaging study on the dissociative ionization of cold S F6 molecules, providing complete, unbiased kinetic energy distributions for all significant product ions. Analysis of these distributions suggests that fragmentation following single ionization proceeds via formation of S F5 + or S F3 + ions that then dissociate in a statistical manner through loss of F atoms or F2, until most internal energy has been liberated. Similarly, formation of stable dications is consistent with initial formation of S F4 2 + ions, which then dissociate on a longer time scale. These data allow a comparison between electron ionization and photoionization dynamics, revealing similar dynamical behavior. In parallel with the ion kinetic energy distributions, the velocity-map imaging approach provides a set of partial ionization cross sections for all detected ionic fragments over an electron energy range of 50-100 eV, providing partial cross sections for S2 +, and enables the cross sections for S F4 2 + from S F+ to be resolved.

Fluid and hybrid models for streamers

NASA Astrophysics Data System (ADS)

Bonaventura, Zdeněk

2016-09-01

Streamers are contracted ionizing waves with self-generated field enhancement that propagate into a low-ionized medium exposed to high electric field leaving filamentary trails of plasma behind. The widely used model to study streamer dynamics is based on drift-diffusion equations for electrons and ions, assuming local field approximation, coupled with Poisson's equation. For problems where presence of energetic electrons become important a fluid approach needs to be extended by a particle model, accompanied also with Monte Carlo Collision technique, that takes care of motion of these electrons. A combined fluid-particle approach is used to study an influence of surface emission processes on a fast-pulsed dielectric barrier discharge in air at atmospheric pressure. It is found that fluid-only model predicts substantially faster reignition dynamics compared to coupled fluid-particle model. Furthermore, a hybrid model can be created in which the population of electrons is divided in the energy space into two distinct groups: (1) low energy `bulk' electrons that are treated with fluid model, and (2) high energy `beam' electrons, followed as particles. The hybrid model is then capable not only to deal with streamer discharges in laboratory conditions, but also allows us to study electron acceleration in streamer zone of lighting leaders. There, the production of fast electrons from streamers is investigated, since these (runaway) electrons act as seeds for the relativistic runaway electron avalanche (RREA) mechanism, important for high-energy atmospheric physics phenomena. Results suggest that high energy electrons effect the streamer propagation, namely the velocity, the peak electric field, and thus also the production rate of runaway electrons. This work has been supported by the Czech Science Foundation research project 15-04023S.

Supercritical fluid chromatography coupled with in-source atmospheric pressure ionization hydrogen/deuterium exchange mass spectrometry for compound speciation.

PubMed

Cho, Yunju; Choi, Man-Ho; Kim, Byungjoo; Kim, Sunghwan

2016-04-29

An experimental setup for the speciation of compounds by hydrogen/deuterium exchange (HDX) with atmospheric pressure ionization while performing chromatographic separation is presented. The proposed experimental setup combines the high performance supercritical fluid chromatography (SFC) system that can be readily used as an inlet for mass spectrometry (MS) and atmospheric pressure photo ionization (APPI) or atmospheric pressure chemical ionization (APCI) HDX. This combination overcomes the limitation of an approach using conventional liquid chromatography (LC) by minimizing the amount of deuterium solvents used for separation. In the SFC separation, supercritical CO2 was used as a major component of the mobile phase, and methanol was used as a minor co-solvent. By using deuterated methanol (CH3OD), AP HDX was achieved during SFC separation. To prove the concept, thirty one nitrogen- and/or oxygen-containing standard compounds were analyzed by SFC-AP HDX MS. The compounds were successfully speciated from the obtained SFC-MS spectra. The exchange ions were observed with as low as 1% of CH3OD in the mobile phase, and separation could be performed within approximately 20min using approximately 0.24 mL of CH3OD. The results showed that SFC separation and APPI/APCI HDX could be successfully performed using the suggested method. Copyright © 2016 Elsevier B.V. All rights reserved.

Attosecond Spectroscopy Probing Electron Correlation Dynamics

NASA Astrophysics Data System (ADS)

Winney, Alexander H.

Electrons are the driving force behind every chemical reaction. The exchange, ionization, or even relaxation of electrons is behind every bond broken or formed. According to the Bohr model of the atom, it takes an electron 150 as to orbit a proton[6]. With this as a unit time scale for an electron, it is clear that a pulse duration of several femtoseconds will not be sufficient to understanding electron dynamics. Our work demonstrates both technical and scientific achievements that push the boundaries of attosecond dynamics. TDSE studies show that amplification the yield of high harmonic generation (HHG) may be possible with transverse confinement of the electron. XUV-pump-XUV-probe shows that the yield of APT train can be sufficient for 2-photon double ionization studies. A zero dead-time detection system allows for the measurement of state-resolved double ionization for the first time. Exploiting attosecond angular streaking[7] probes sequential and non-sequential double ionization via electron-electron correlations with attosecond time resolution. Finally, using recoil frame momentum correlation, the fast dissociation of CH 3I reveals important orbital ionization dynamics of non-dissociative & dissociative, single & double ionization.

The Interaction Between Accretion from the Interstellar Medium and Accretion from the Evolved Binary Component in Barium Stars

NASA Astrophysics Data System (ADS)

Jeong, Yeuncheol; Yushchenko, Alexander V.; Doikov, Dmytry N.

2018-03-01

The reanalysis of the previously published abundance pattern of mild barium star HD202109 (ζ Cyg) and the chemical compositions of 129 thin disk barium stars facilitated the search for possible correlations of different stellar parameters with second ionization potentials of chemical elements. Results show that three valuable correlations exist in the atmospheres of barium stars. The first is the relationship between relative abundances and second ionization potentials. The second is the age dependence of mean correlation coefficients of relative abundances vs. second ionization potentials, and the third one is the changes in correlation coefficients of relative abundances vs. second ionization potentials as a function of stellar spatial velocities and overabundances of s-process elements. These findings demonstrate the possibility of hydrogen and helium accretion from the interstellar medium on the atmospheres of barium stars.

Characterization of direct-current atmospheric-pressure discharges useful for ambient desorption/ionization mass spectrometry.

PubMed

Shelley, Jacob T; Wiley, Joshua S; Chan, George C Y; Schilling, Gregory D; Ray, Steven J; Hieftje, Gary M

2009-05-01

Two relatively new ambient ionization sources, direct analysis in real time (DART) and the flowing atmospheric-pressure afterglow (FAPA), use direct current, atmospheric-pressure discharges to produce reagent ions for the direct ionization of a sample. Although at a first glance these two sources appear similar, a fundamental study reveals otherwise. Specifically, DART was found to operate with a corona-to-glow transition (C-G) discharge whereas the FAPA was found to operate with a glow-to-arc transition (G-A) discharge. The characteristics of both discharges were evaluated on the basis of four factors: reagent-ion production, response to a model analyte (ferrocene), infrared (IR) thermography of the gas used for desorption and ionization, and spatial emission characteristics. The G-A discharge produced a greater abundance and a wider variety of reagent ions than the C-G discharge. In addition, the discharges yielded different adducts and signal strengths for ferrocene. It was also found that the gas exiting the discharge chamber reached a maximum of 235 degrees C and 55 degrees C for the G-A and C-G discharges, respectively. Finally, spatially resolved emission maps of both discharges showed clear differences for N(2)(+) and O(I). These findings demonstrate that the discharges used by FAPA and DART are fundamentally different and should have different optimal applications for ambient desorption/ionization mass spectrometry (ADI-MS).

Tunable Ionization Modes of a Flowing Atmospheric-Pressure Afterglow (FAPA) Ambient Ionization Source.

PubMed

Badal, Sunil P; Michalak, Shawn D; Chan, George C-Y; You, Yi; Shelley, Jacob T

2016-04-05

Plasma-based ambient desorption/ionization sources are versatile in that they enable direct ionization of gaseous samples as well as desorption/ionization of analytes from liquid and solid samples. However, ionization matrix effects, caused by competitive ionization processes, can worsen sensitivity or even inhibit detection all together. The present study is focused on expanding the analytical capabilities of the flowing atmospheric-pressure afterglow (FAPA) source by exploring additional types of ionization chemistry. Specifically, it was found that the abundance and type of reagent ions produced by the FAPA source and, thus, the corresponding ionization pathways of analytes, can be altered by changing the source working conditions. High abundance of proton-transfer reagent ions was observed with relatively high gas flow rates and low discharge currents. Conversely, charge-transfer reagent species were most abundant at low gas flows and high discharge currents. A rather nonpolar model analyte, biphenyl, was found to significantly change ionization pathway based on source operating parameters. Different analyte ions (e.g., MH(+) via proton-transfer and M(+.) via charge-transfer) were formed under unique operating parameters demonstrating two different operating regimes. These tunable ionization modes of the FAPA were used to enable or enhance detection of analytes which traditionally exhibit low-sensitivity in plasma-based ADI-MS analyses. In one example, 2,2'-dichloroquaterphenyl was detected under charge-transfer FAPA conditions, which were difficult or impossible to detect with proton-transfer FAPA or direct analysis in real-time (DART). Overall, this unique mode of operation increases the number and range of detectable analytes and has the potential to lessen ionization matrix effects in ADI-MS analyses.

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwartz, Andrew J.; Shelley, Jacob T.; Walton, Courtney L.

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-likemore » spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.« less

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge

DOE PAGES

Schwartz, Andrew J.; Shelley, Jacob T.; Walton, Courtney L.; ...

2016-06-27

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here in this paper, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-likemore » spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma.« less

Natural Hazards of the Space Environment

NASA Technical Reports Server (NTRS)

Evans, Steven W.; Kross, Dennis A. (Technical Monitor)

2000-01-01

Spacecraft in Low Earth Orbit (LEO) are subject to numerous environmental hazards. Here I'll briefly discuss three environment factors that pose acute threats to the survival of spacecraft systems and crew: atmospheric drag, impacts by meteoroids and orbital debris, and ionizing radiation. Atmospheric drag continuously opposes the orbital motion of a satellite, causing the orbit to decay. This decay will lead to reentry if not countered by reboost maneuvers. Orbital debris is a by-product of man's activities in space, and consists of objects ranging in size from miniscule paint chips to spent rocket stages and dead satellites. Ionizing radiation experienced in LEO has several components: geomagnetically trapped protons and electrons (Van Allen belts); energetic solar particles; galactic cosmic rays; and albedo neutrons. These particles can have several types of prompt harmful effects on equipment and crew, from single-event upsets, latchup, and burnout of electronics, to lethal doses to crew.All three types of prompt threat show some dependence on the solar activity cycle. Atmospheric drag mitigation and large debris avoidance require propulsive maneuvers. M/OD and ionizing radiation require some form of shielding for crew and sensitive equipment. Limiting exposure time is a mitigation technique for ionizing radiation and meteor streams.

Simultaneous extraction of acetylsalicylic acid and salicylic acid from human plasma and simultaneous estimation by liquid chromatography and atmospheric pressure chemical ionization/tandem mass spectrometry detection. Application to a pharmacokinetic study.

PubMed

Nirogi, Ramakrishna; Kandikere, Vishwottam; Mudigonda, Koteshwara; Ajjala, Devender; Suraneni, Ramakrishna; Thoddi, Parthasarathi

2011-01-01

A simple analytical method using liquid chromatography-tandem mass spectrometry (LC-MS/MS) in atmospheric chemical ionization mode (APCI) for the simultaneous estimation of acetylsalicylic acid (ASA, CAS 50-78-2) and its active metabolite salicylic acid (SA, CAS 69-72-7) in human plasma has been developed and validated. ASA and SA were analyzed simultaneously despite differences in plasma concentration ranges of ASA and SA after oral administration of ASA. In spite of having different chemical, ionization and chromatographic properties, ASA and SA were extracted simultaneously from the plasma sample using acetonitrile protein precipitation followed by liquid-liquid extraction. The analytes were separated on a reversed phase column with rapid gradient program using mobile phase consisting of ammonium acetate buffer and methanol. The structural analogue diclofenac was used as an internal standard. The multiple reaction monitoring (MRM) transitions m/z 179 --> 137 for ASA, m/z 137 --> 65 for SA and m/z 294 --> 250 for IS were used. The assay exhibited a linear dynamic range of 0.02-10 microg/mL for ASA and 0.1-50 microg/mL for SA. The between-batch precision (%CV) ranged from 2.1 to 7.9% for ASA and from 0.2 to 5.2% for SA. The between-batch accuracy ranged from 95.4 to 96.7% for ASA and from 94.6 to 111.3% for SA. The validated method was successfully applied for the evaluation of pharmacokinetics of ASA after single oral administration of 650 mg test formulation versus two 325 mg reference formulations of ASA in human subjects.

Non-thermal hydrogen atoms in the terrestrial upper thermosphere.

PubMed

Qin, Jianqi; Waldrop, Lara

2016-12-06

Model predictions of the distribution and dynamical transport of hydrogen atoms in the terrestrial atmosphere have long-standing discrepancies with ultraviolet remote sensing measurements, indicating likely deficiencies in conventional theories regarding this crucial atmospheric constituent. Here we report the existence of non-thermal hydrogen atoms that are much hotter than the ambient oxygen atoms in the upper thermosphere. Analysis of satellite measurements indicates that the upper thermospheric hydrogen temperature, more precisely the mean kinetic energy of the atomic hydrogen population, increases significantly with declining solar activity, contrary to contemporary understanding of thermospheric behaviour. The existence of hot hydrogen atoms in the upper thermosphere, which is the key to reconciling model predictions and observations, is likely a consequence of low atomic oxygen density leading to incomplete collisional thermalization of the hydrogen population following its kinetic energization through interactions with hot atomic or ionized constituents in the ionosphere, plasmasphere or magnetosphere.

Non-thermal hydrogen atoms in the terrestrial upper thermosphere

PubMed Central

Qin, Jianqi; Waldrop, Lara

2016-01-01

Model predictions of the distribution and dynamical transport of hydrogen atoms in the terrestrial atmosphere have long-standing discrepancies with ultraviolet remote sensing measurements, indicating likely deficiencies in conventional theories regarding this crucial atmospheric constituent. Here we report the existence of non-thermal hydrogen atoms that are much hotter than the ambient oxygen atoms in the upper thermosphere. Analysis of satellite measurements indicates that the upper thermospheric hydrogen temperature, more precisely the mean kinetic energy of the atomic hydrogen population, increases significantly with declining solar activity, contrary to contemporary understanding of thermospheric behaviour. The existence of hot hydrogen atoms in the upper thermosphere, which is the key to reconciling model predictions and observations, is likely a consequence of low atomic oxygen density leading to incomplete collisional thermalization of the hydrogen population following its kinetic energization through interactions with hot atomic or ionized constituents in the ionosphere, plasmasphere or magnetosphere. PMID:27922018

Plasma diagnostics of non-equilibrium atmospheric plasma jets

NASA Astrophysics Data System (ADS)

Shashurin, Alexey; Scott, David; Keidar, Michael; Shneider, Mikhail

2014-10-01

Intensive development and biomedical application of non-equilibrium atmospheric plasma jet (NEAPJ) facilitates rapid growth of the plasma medicine field. The NEAPJ facility utilized at the George Washington University (GWU) demonstrated efficacy for treatment of various cancer types (lung, bladder, breast, head, neck, brain and skin). In this work we review recent advances of the research conducted at GWU concerned with the development of NEAPJ diagnostics including Rayleigh Microwave Scattering setup, method of streamer scattering on DC potential, Rogowski coils, ICCD camera and optical emission spectroscopy. These tools allow conducting temporally-resolved measurements of plasma density, electrical potential, charge and size of the streamer head, electrical currents flowing though the jet, ionization front propagation speed etc. Transient dynamics of plasma and discharge parameters will be considered and physical processes involved in the discharge will be analyzed including streamer breakdown, electrical coupling of the streamer tip with discharge electrodes, factors determining NEAPJ length, cross-sectional shape and propagation path etc.

Direct analysis in real time--a critical review on DART-MS.

PubMed

Gross, Jürgen H

2014-01-01

Direct analysis in real time mass spectrometry (DART-MS) has become an established technique for rapid mass spectral analysis of a large variety of samples. DART-MS is capable of analyzing the sample at atmospheric pressure, essentially in the open laboratory environment. DART-MS can be applied to compounds that have been deposited or adsorbed on to surfaces or that are being desorbed therefrom into the atmosphere. This makes DART-MS suitable and well-known for analysis of ingredients of plant materials, pesticide monitoring on vegetables, forensic and safety applications such as screening for traces of explosives, warfare agents, or illicit drugs on luggage, clothes, or bank notes, etc. DART can also be used for analysis of either solid or liquid bulk materials, as may be required in quality control, or to quickly investigate the identity of a compound from chemical synthesis. Even living organisms can be subjected to DART-MS. Driven by different needs in analytical practice, the combination of the DART ionization source and interface can be configured in multiple geometries and with various accessories to adapt the setup as required. Analysis by DART-MS relies on some sort of gas-phase ionization mechanism. In DART, initial generation of the ionizing species is by use of a corona discharge in a pure helium atmosphere which delivers excited helium atoms that, upon their release into the atmosphere, will initiate a cascade of gas-phase reactions. In the end, this results in reagent ions created from atmospheric water or (solvent) vapor in the vicinity of the surface subject to analysis where they effect a chemical ionization process. DART ionization processes may generate positive or negative ions, predominantly even-electron species, but odd-electron species do also occur. The prevailing process of analyte ion formation from a given sample is highly dependent on analyte properties.

Plasma density enhancements created by the ionization of the Earth's upper atmosphere by artificial electron beams

NASA Technical Reports Server (NTRS)

Neubert, Torsten; Banks, Peter M.

1990-01-01

Analytical calculations and experimental observations relating to the interaction with the Earth's upper atmosphere of electron beams emitted from low altitude spacecraft are presented. The problem is described by two coupled nonlinear differential equations in the up-going (along a magnetic field line) and down-going differential energy flux. The equations are solved numerically, using the MSIS atmospheric model and the IRI ionospheric model. The results form the model compare well with recent observations from the CHARGE 2 sounding rocket experiment. Two aspects of the beam-neutral atmosphere interaction are discussed. First, the limits on the electron beam current that can be emitted from a spacecraft without substantial spacecraft charging are investigated. This is important because the charging of the spacecraft to positive potentials limits the current and the escape energy of the beam electrons and thereby limits the ionization of the neutral atmosphere. As an example, we find from CHARGE 2 observations and from the model calculations that below about 180 km, secondary electrons generated through the ionization of the neutral atmosphere by 1 to 10 keV electron beams from sounding rockets, completely balance the beam current, thereby allowing the emission of very high beam currents. Second, the amount of plasma production in the beam-streak is discussed. Results are shown for selected values of the beam energy, spacecraft velocity, and spacecraft altitude.

High molecular weight non-polar hydrocarbons as pure model substances and in motor oil samples can be ionized without fragmentation by atmospheric pressure chemical ionization mass spectrometry.

PubMed

Hourani, Nadim; Kuhnert, Nikolai

2012-10-15

High molecular weight non-polar hydrocarbons are still difficult to detect by mass spectrometry. Although several studies have targeted this problem, lack of good self-ionization has limited the ability of mass spectrometry to examine these hydrocarbons. Failure to control ion generation in the atmospheric pressure chemical ionization (APCI) source hampers the detection of intact stable gas-phase ions of non-polar hydrocarbon in mass spectrometry. Seventeen non-volatile non-polar hydrocarbons, reported to be difficult to ionize, were examined by an optimized APCI methodology using nitrogen as the reagent gas. All these analytes were successfully ionized as abundant and intact stable [M-H](+) ions without the use of any derivatization or adduct chemistry and without significant fragmentation. Application of the method to real-life hydrocarbon mixtures like light shredder waste and car motor oil was demonstrated. Despite numerous reports to the contrary, it is possible to ionize high molecular weight non-polar hydrocarbons by APCI, omitting the use of additives. This finding represents a significant step towards extending the applicability of mass spectrometry to non-polar hydrocarbon analyses in crude oil, petrochemical products, waste or food. Copyright © 2012 John Wiley & Sons, Ltd.

Choosing between atmospheric pressure chemical ionization and electrospray ionization interfaces for the HPLC/MS analysis of pesticides

USGS Publications Warehouse

Thurman, E.M.; Ferrer, I.; Barcelo, D.

2001-01-01

An evaluation of over 75 pesticides by high-performance liquid chromatography/mass spectrometry (HPLC/MS) clearly shows that different classes of pesticides are more sensitive using either atmospheric pressure chemical ionization (APCI) or electrospray ionization (ESI). For example, neutral and basic pesticides (phenylureas, triazines) are more sensitive using APCI (especially positive ion). While cationic and anionic herbicides (bipyridylium ions, sulfonic acids) are more sensitive using ESI (especially negative ion). These data are expressed graphically in a figure called an ionization-continuum diagram, which shows that protonation in the gas phase (proton affinity) and polarity in solution, expressed as proton addition or subtraction (pKa), is useful in selecting APCI or ESI. Furthermore, sodium adduct formation commonly occurs using positive ion ESI but not using positive ion APCI, which reflects the different mechanisms of ionization and strengthens the usefulness of the ionization-continuum diagram. The data also show that the concept of "wrong-way around" ESI (the sensitivity of acidic pesticides in an acidic mobile phase) is a useful modification of simple pKa theory for mobile-phase selection. Finally, this finding is used to enhance the chromatographic separation of oxanilic and sulfonic acid herbicides while maintaining good sensitivity in LC/MS using ESI negative.

Minimizing thermal degradation in gas chromatographic quantitation of pentaerythritol tetranitrate.

PubMed

Lubrano, Adam L; Field, Christopher R; Newsome, G Asher; Rogers, Duane A; Giordano, Braden C; Johnson, Kevin J

2015-05-15

An analytical method for establishing calibration curves for the quantitation of pentaerythriol tetranitrate (PETN) from sorbent-filled thermal desorption tubes by gas chromatography with electron capture detection (TDS-GC-ECD) was developed. As PETN has been demonstrated to thermally degrade under typical GC instrument conditions, peaks corresponding to both PETN degradants and molecular PETN are observed. The retention time corresponding to intact PETN was verified by high-resolution mass spectrometry with a flowing atmospheric pressure afterglow (FAPA) ionization source, which enabled soft ionization of intact PETN eluting the GC and subsequent accurate-mass identification. The GC separation parameters were transferred to a conventional GC-ECD instrument where analytical method-induced PETN degradation was further characterized and minimized. A method calibration curve was established by direct liquid deposition of PETN standard solutions onto the glass frit at the head of sorbent-filled thermal desorption tubes. Two local, linear relationships between detector response and PETN concentration were observed, with a total dynamic range of 0.25-25ng. Published by Elsevier B.V.

Depolarizing collisions with hydrogen: Neutral and singly ionized alkaline earths

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manso Sainz, Rafael; Ramos, Andrés Asensio; Bueno, Javier Trujillo

2014-06-20

Depolarizing collisions are elastic or quasielastic collisions that equalize the populations and destroy the coherence between the magnetic sublevels of atomic levels. In astrophysical plasmas, the main depolarizing collider is neutral hydrogen. We consider depolarizing rates on the lowest levels of neutral and singly ionized alkali earths Mg I, Sr I, Ba I, Mg II, Ca II, and Ba II, due to collisions with H°. We compute ab initio potential curves of the atom-H° system and solve the quantum mechanical dynamics. From the scattering amplitudes, we calculate the depolarizing rates for Maxwellian distributions of colliders at temperatures T ≤ 10,000more » K. A comparative analysis of our results and previous calculations in the literature is completed. We discuss the effect of these rates on the formation of scattering polarization patterns of resonant lines of alkali earths in the solar atmosphere, and their effect on Hanle effect diagnostics of solar magnetic fields.« less

Combination of electrospray ionization, atmospheric pressure photoionization and laser desorption ionization Fourier transform ion cyclotronic resonance mass spectrometry for the investigation of complex mixtures - Application to the petroleomic analysis of bio-oils.

PubMed

Hertzog, Jasmine; Carré, Vincent; Le Brech, Yann; Mackay, Colin Logan; Dufour, Anthony; Mašek, Ondřej; Aubriet, Frédéric

2017-05-29

The comprehensive description of complex mixtures such as bio-oils is required to understand and improve the different processes involved during biological, environmental or industrial operation. In this context, we have to consider how different ionization sources can improve a non-targeted approach. Thus, the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) has been coupled to electrospray ionization (ESI), laser desorption ionization (LDI) and atmospheric pressure photoionization (APPI) to characterize an oak pyrolysis bio-oil. Close to 90% of the all 4500 compound formulae has been attributed to C x H y O z with similar oxygen class compound distribution. Nevertheless, their relative abundance in respect with their double bound equivalent (DBE) value has evidenced significant differences depending on the ion source used. ESI has allowed compounds with low DBE but more oxygen atoms to be ionized. APPI has demonstrated the efficient ionization of less polar compounds (high DBE values and less oxygen atoms). The LDI behavior of bio-oils has been considered intermediate in terms of DBE and oxygen amounts but it has also been demonstrated that a significant part of the features are specifically detected by this ionization method. Thus, the complementarity of three different ionization sources has been successfully demonstrated for the exhaustive characterization by petroleomic approach of a complex mixture. Copyright © 2017 Elsevier B.V. All rights reserved.

Sampling and analyte enrichment strategies for ambient mass spectrometry.

PubMed

Li, Xianjiang; Ma, Wen; Li, Hongmei; Ai, Wanpeng; Bai, Yu; Liu, Huwei

2018-01-01

Ambient mass spectrometry provides great convenience for fast screening, and has showed promising potential in analytical chemistry. However, its relatively low sensitivity seriously restricts its practical utility in trace compound analysis. In this review, we summarize the sampling and analyte enrichment strategies coupled with nine modes of representative ambient mass spectrometry (desorption electrospray ionization, paper vhspray ionization, wooden-tip spray ionization, probe electrospray ionization, coated blade spray ionization, direct analysis in real time, desorption corona beam ionization, dielectric barrier discharge ionization, and atmospheric-pressure solids analysis probe) that have dramatically increased the detection sensitivity. We believe that these advances will promote routine use of ambient mass spectrometry. Graphical abstract Scheme of sampling stretagies for ambient mass spectrometry.

Ion Chemistry in Atmospheric and Astrophysical Plasmas

NASA Technical Reports Server (NTRS)

Dalgarno, A.; Fox, J. L.

1994-01-01

There are many differences and also remarkable similarities between the ion chemistry and physics of planetary ionospheres and the ion chemistry and physics of astronomical environments beyond the solar system. In the early Universe, an expanded cooling gas of hydrogen and helium was embedded in the cosmic background radiation field and ionized by it. As the Universe cooled by adiabatic expansion, recombination occurred and molecular formation was driven by catalytic reactions involving the relict electrons and protons. Similar chemical processes are effective in the ionized zones of gaseous and planetary nebulae and in stellar winds where the ionization is due to radiation from the central stars, in the envelopes of supernovae where the ionization is initiated by the deposition of gamma-rays, in dissociative shocks where the ionization arises from electron impacts in a hot gas and in quasar broad-line region clouds where the quasar is responsible for the ionization. At high altitudes in the atmospheres of the Jovian planets, the main constituents are hydrogen and helium and the ion chemistry and physics is determined by the same processes, the source of the ionization being solar ultraviolet radiation and cosmic rays. After the collapse of the first distinct astronomical entities to emerge from the uniform flow, heavy elements were created by nuclear burning in the cores of the collapsed objects and distributed throughout the Universe by winds and explosions. The chemistry and physics became more complicated. Over 90 distinct molecular species have been identified in interstellar clouds where they are ionized globally by cosmic ray impacts and locally by radiation and shocks associated with star formation and evolution. Complex molecules have also been found in circumstellar shells of evolved stars. At intermediate and low altitudes in the Jovian atmospheres, the ion chemistry is complicated by the increasing abundance of heavy elements such as carbon, and an extensive array of complex molecules has been predicted. Reactions involving heavy elements dominate the structure of the ionspheres of the terrestrial planets and the satellites Titan and Triton.

FAST TRACK COMMUNICATION: Effects of Penning ionization on the discharge patterns of atmospheric pressure plasma jets

NASA Astrophysics Data System (ADS)

Li, Qing; Zhu, Wen-Chao; Zhu, Xi-Ming; Pu, Yi-Kang

2010-09-01

Atmospheric pressure plasma jets, generated in a coaxial dielectric barrier discharge configuration, have been investigated with different flowing gases. Discharge patterns in different tube regions were compared in the flowing gases of helium, neon and krypton. To explain the difference of these discharge patterns, a theoretical analysis is presented to reveal the possible basic processes. A comparison of experimental and theoretical results identifies that Penning ionization is mainly responsible for the discharge patterns of helium and neon plasma jets.

The EUV Emission in Comet-Solar Corona Interactions

NASA Technical Reports Server (NTRS)

Bryans, Paul; Pesnell, William Dean; Schrijver, Carolus J.; Brown, John C.; Battams, Karl; Saint-Hilaire, Pasal; Liu, Wei; Hudson, Hugh S.

2011-01-01

The Atmospheric Imaging Assembly (AlA) on the Solar Dynamics Observatory (SDO) viewed a comet as it passed through the solar corona on 2011 July 5. This was the first sighting of a comet by a EUV telescope. For 20 minutes, enhanced emission in several of the AlA wavelength bands marked the path of the comet. We explain this EUV emission by considering the evolution of the cometary atmosphere as it interacts with the ambient solar atmosphere. Water ice in the comet rapidly sublimates as it approaches the Sun. This water vapor is then photodissociated, primarily by Ly-alpha, by the solar radiation field to create atomic Hand O. Other molecules present in the comet also evaporate and dissociate to give atomic Fe and other metals. Subsequent ionization of these atoms can be achieved by a number of means, including photoionization, electron impact, and charge exchange with coronal protons and other highly-charged species. Finally, particles from the cometary atmosphere are thermalized to the background temperature of the corona. Each step could cause emission in the AlA bandpasses. We will report here on their relative contribution to the emission seen in the AlA telescopes.

Correlation-driven charge migration following double ionization and attosecond transient absorption spectroscopy

NASA Astrophysics Data System (ADS)

Hollstein, Maximilian; Santra, Robin; Pfannkuche, Daniela

2017-05-01

We theoretically investigate charge migration following prompt double ionization. Thereby, we extend the concept of correlation-driven charge migration, which was introduced by Cederbaum and coworkers for single ionization [Chem. Phys. Lett. 307, 205 (1999), 10.1016/S0009-2614(99)00508-4], to doubly ionized molecules. This allows us to demonstrate that compared to singly ionized molecules, in multiply ionized molecules, electron dynamics originating from electronic relaxation and correlation are particularly prominent. In addition, we also discuss how these correlation-driven electron dynamics might be evidenced and traced experimentally using attosecond transient absorption spectroscopy. For this purpose, we determine the time-resolved absorption cross section and find that the correlated electron dynamics discussed are reflected in it with exceptionally great detail. Strikingly, we find that features in the cross section can be traced back to electron hole populations and time-dependent partial charges and hence, can be interpreted with surprising ease. By taking advantage of element-specific core-to-valence transitions even atomic spatial resolution can be achieved. Thus, with the theoretical considerations presented, not only do we predict particularly diverse and correlated electron dynamics in molecules to follow prompt multiple ionization but we also identify a promising route towards their experimental investigation.

Mesospheric Dynamical Changes Induced by the Solar Proton Events in October-November 2003

NASA Technical Reports Server (NTRS)

Jackman, Charles H.; Roble, Raymond G.; Fleming, Eric L.

2007-01-01

The very large solar storms in October-November 2003 caused solar proton events (SPEs) at the Earth that impacted the upper atmospheric polar cap regions. The Thermosphere Ionosphere Mesosphere Electrodynamic General Circulation Model (TIME-GCM) was used to study the atmospheric dynamical influence of the solar protons that occurred in Oct-Nov 2003, the fourth largest period of SPEs measured in the past 40 years. The highly energetic solar protons caused ionization, as well as dissociation processes, and ultimately produced odd hydrogen (HOx) and odd nitrogen (NOy). Significant short-lived ozone decreases (10-70%) followed these enhancements of HOx and NOy and led to a cooling of most of the lower mesosphere. This cooling caused an atmospheric circulation change that led to adiabatic heating of the upper mesosphere. Temperature changes up to plus or minus 2.6 K were computed as well as wind (zonal, meridional, vertical) perturbations up to 20-25% of the background winds as a result of 22 the solar protons. The solar proton-induced mesospheric temperature and wind perturbations diminished over a period of 4-6 weeks after the SPEs. The Joule heating in the mesosphere, induced by the solar protons, was computed to be relatively insignificant for these solar storms with most of the temperature and circulation perturbations caused by ozone depletion in the sunlit hemisphere.

Mass Spectrometry of Single Particles Levitated in an Electrodynamic Balance: Applications to Laboratory Atmospheric Chemistry Research

NASA Astrophysics Data System (ADS)

Birdsall, A.; Krieger, U. K.; Keutsch, F. N.

2017-12-01

Dynamic changes to atmospheric aerosol particle composition (e.g., originating from evaporation/condensation, oxidative aging, or aqueous-phase chemical reactions) impact particle properties with importance for understanding particle effects on climate and human health. These changes can take place over the entire lifetime of an atmospheric particle, which can extend over multiple days. Previous laboratory studies of such processes have included analyzing single particles suspended in a levitation device, such as an electrodynamic balance (EDB), an optical levitator, or an acoustic trap, using optical detection techniques. However, studying chemically complex systems can require an analytical method, such as mass spectrometry, that provides more molecular specificity. Existing work coupling particle levitation with mass spectrometry is more limited and largely has consisted of acoustic levitation of millimeter-sized droplets.In this work an EDB has been coupled with a custom-built ionization source and commercial time-of-flight mass spectrometer (MS) as a platform for laboratory atmospheric chemistry research. Single charged particles (radius 10 μm) have been injected into an EDB, levitated for an arbitrarily long period of time, and then transferred to a vaporization-corona discharge ionization region for MS analysis. By analyzing a series of particles of identical composition, residing in the controlled environment of the EDB for varying times, we can trace the chemical evolution of a particle over hours or days, appropriate timescales for understanding transformations of atmospheric particles.To prove the concept of our EDB-MS system, we have studied the evaporation of particles consisting of polyethylene glycol (PEG) molecules of mixed chain lengths, used as a benchmark system. Our system can quantify the composition of single particles (see Figure for sample spectrum of a single PEG-200 particle: PEG parent ions labeled with m/z, known PEG fragment ions labeled with *). Furthermore, our measured evaporation rates are consistent with a kinetic model. We will discuss future types of experiments enabled by EDB-MS, by allowing detailed chemical changes of a particle in a controlled laboratory environment to be monitored on timescales mimicking those of particles in the atmosphere.

Photoemission and photoionization time delays and rates

PubMed Central

Gallmann, L.; Jordan, I.; Wörner, H. J.; Castiglioni, L.; Hengsberger, M.; Osterwalder, J.; Arrell, C. A.; Chergui, M.; Liberatore, E.; Rothlisberger, U.; Keller, U.

2017-01-01

Ionization and, in particular, ionization through the interaction with light play an important role in fundamental processes in physics, chemistry, and biology. In recent years, we have seen tremendous advances in our ability to measure the dynamics of photo-induced ionization in various systems in the gas, liquid, or solid phase. In this review, we will define the parameters used for quantifying these dynamics. We give a brief overview of some of the most important ionization processes and how to resolve the associated time delays and rates. With regard to time delays, we ask the question: how long does it take to remove an electron from an atom, molecule, or solid? With regard to rates, we ask the question: how many electrons are emitted in a given unit of time? We present state-of-the-art results on ionization and photoemission time delays and rates. Our review starts with the simplest physical systems: the attosecond dynamics of single-photon and tunnel ionization of atoms in the gas phase. We then extend the discussion to molecular gases and ionization of liquid targets. Finally, we present the measurements of ionization delays in femto- and attosecond photoemission from the solid–vacuum interface. PMID:29308414

A physics-based model for the ionization of samarium by the MOSC chemical releases in the upper atmosphere

NASA Astrophysics Data System (ADS)

Bernhardt, Paul A.; Siefring, Carl L.; Briczinski, Stanley J.; Viggiano, Albert; Caton, Ronald G.; Pedersen, Todd R.; Holmes, Jeffrey M.; Ard, Shaun; Shuman, Nicholas; Groves, Keith M.

2017-05-01

Atomic samarium has been injected into the neutral atmosphere for production of electron clouds that modify the ionosphere. These electron clouds may be used as high-frequency radio wave reflectors or for control of the electrodynamics of the F region. A self-consistent model for the photochemical reactions of Samarium vapor cloud released into the upper atmosphere has been developed and compared with the Metal Oxide Space Cloud (MOSC) experimental observations. The release initially produces a dense plasma cloud that that is rapidly reduced by dissociative recombination and diffusive expansion. The spectral emissions from the release cover the ultraviolet to the near infrared band with contributions from solar fluorescence of the atomic, molecular, and ionized components of the artificial density cloud. Barium releases in sunlight are more efficient than Samarium releases in sunlight for production of dense ionization clouds. Samarium may be of interest for nighttime releases but the artificial electron cloud is limited by recombination with the samarium oxide ion.

Comparison of free radicals formation induced by cold atmospheric plasma, ultrasound, and ionizing radiation.

PubMed

Rehman, Mati Ur; Jawaid, Paras; Uchiyama, Hidefumi; Kondo, Takashi

2016-09-01

Plasma medicine is increasingly recognized interdisciplinary field combining engineering, physics, biochemistry and life sciences. Plasma is classified into two categories based on the temperature applied, namely "thermal" and "non-thermal" (i.e., cold atmospheric plasma). Non-thermal or cold atmospheric plasma (CAP) is produced by applying high voltage electric field at low pressures and power. The chemical effects of cold atmospheric plasma in aqueous solution are attributed to high voltage discharge and gas flow, which is transported rapidly on the liquid surface. The argon-cold atmospheric plasma (Ar-CAP) induces efficient reactive oxygen species (ROS) in aqueous solutions without thermal decomposition. Their formation has been confirmed by electron paramagnetic resonance (EPR) spin trapping, which is reviewed here. The similarities and differences between the plasma chemistry, sonochemistry, and radiation chemistry are explained. Further, the evidence for free radical formation in the liquid phase and their role in the biological effects induced by cold atmospheric plasma, ultrasound and ionizing radiation are discussed. Copyright © 2016 Elsevier Inc. All rights reserved.

Magnetic Reconnection in the Solar Chromosphere

NASA Astrophysics Data System (ADS)

Lukin, Vyacheslav S.; Ni, Lei; Murphy, Nicholas Arnold

2017-08-01

We report on the most recent efforts to accurately and self-consistently model magnetic reconnection processes in the context of the solar chromosphere. The solar chromosphere is a notoriously complex and highly dynamic boundary layer of the solar atmosphere where local variations in the plasma parameters can be of the order of the mean values. At the same time, the interdependence of the physical processes such as magnetic field evolution, local and global energy transfer between internal and electromagnetic plasma energy, radiation transport, plasma reactivity, and dissipation mechanisms make it a particularly difficult system to self-consistently model and understand. Several recent studies have focused on the micro-physics of multi-fluid magnetic reconnection at magnetic nulls in the weakly ionized plasma environment of the lower chromosphere[1-3]. Here, we extend the previous work by considering a range of spatial scales and magnetic field strengths in a configuration with component magnetic reconnection, i.e., for magnetic reconnection with a guide field. We show that in all cases the non-equilibrium reactivity of the plasma and the dynamic interaction among the plasma processes play important roles in determining the structure of the reconnection region. We also speculate as to the possible observables of chromospheric magnetic reconnection and the likely plasma conditions required for generation of Ellerman and IRIS bombs.[1] Leake, Lukin, Linton, and Meier, “Multi-fluid simulations of chromospheric magnetic reconnection in a weakly ionized reacting plasma,” ApJ 760 (2012).[2] Leake, Lukin, and Linton, “Magnetic reconnection in a weakly ionized plasma,” PoP 20 (2013).[3] Murphy and Lukin, “Asymmetric magnetic reconnection in weakly ionized chromospheric plasmas,” ApJ 805 (2015).[*Any opinion, findings, and conclusions or recommendations expressed in this material are those of the authors and do not necessarily reflect the views of the National Science Foundation.

The effect of target materials on the propagation of atmospheric-pressure plasma jets

NASA Astrophysics Data System (ADS)

Ji, Longfei; Yan, Wen; Xia, Yang; Liu, Dongping

2018-05-01

The current study is focused on the effect of target materials (quartz plate, copper sheet, and quartz plate with a grounded copper sheet on the back) on the propagation of atmospheric-pressure helium plasma jets. The dynamics of ionization waves (IWs) and the relative amount of reactive oxygen species (OH and O) in the IW front were compared by using spatial and temporal images and relative optical emission spectroscopy. Our measurements show that the targets can significantly affect the propagation and intensity of the IWs. In addition, strong OH emission lines were detected when the IWs impinged upon the damp surface. Numerical simulations have been carried out to explain the experimental observation. The propagation velocity of IWs predicted by the simulation was in good agreement with the experimental results. Simulation results suggest that the density and velocity of IWs mainly depend on the electric field between the high voltage electrode tip and the target. Analysis indicates that the targets could change the electric field distribution between the high voltage electrode and targets and thus affect the dynamics and the density of the IWs, the generation of reactive oxygen species, and the corresponding sterilization efficiency.

Ionization of the Earth's Upper Atmosphere in Large Energetic Particle Events

NASA Astrophysics Data System (ADS)

Wolff, E.; Burrows, J.; Kallenrode, M.; von Koenig, M.; Kuenzi, K. F.; Quack, M.

2001-12-01

Energetic charged particles ionize the upper terrestrial atmosphere. Sofar, chemical consequences of precipitating particles have been discussed for solar protons with energies up to a few hundred MeV. We present a refined model for the interaction of energetic particles with the atmosphere based on a Monte-Carlo simulation. The model includes higher energies and other particle species, such as energetic solar electrons. Results are presented for well-known solar events, such as July 14, 2000, and are extrapolated to extremely large events, such as Carrington's white light flare in 1859, which from ice cores has been identified ass the largest impulsive NO3 event in the interval 1561 -- 1994 (McCracken et al., 2001).

Developing a Vacuum Electrospray Source To Implement Efficient Atmospheric Sampling for Miniature Ion Trap Mass Spectrometer.

PubMed

Yu, Quan; Zhang, Qian; Lu, Xinqiong; Qian, Xiang; Ni, Kai; Wang, Xiaohao

2017-12-05

The performance of a miniature mass spectrometer in atmospheric analysis is closely related to the design of its sampling system. In this study, a simplified vacuum electrospray ionization (VESI) source was developed based on a combination of several techniques, including the discontinuous atmospheric pressure interface, direct capillary sampling, and pneumatic-assisted electrospray. Pulsed air was used as a vital factor to facilitate the operation of electrospray ionization in the vacuum chamber. This VESI device can be used as an efficient atmospheric sampling interface when coupled with a miniature rectilinear ion trap (RIT) mass spectrometer. The developed VESI-RIT instrument enables regular ESI analysis of liquid, and its qualitative and quantitative capabilities have been characterized by using various solution samples. A limit of detection of 8 ppb could be attained for arginine in a methanol solution. In addition, extractive electrospray ionization of organic compounds can be implemented by using the same VESI device, as long as the gas analytes are injected with the pulsed auxiliary air. This methodology can extend the use of the proposed VESI technique to rapid and online analysis of gaseous and volatile samples.

Low-dose ionizing radiation limitations to seed germination: Results from a model linking physiological characteristics and developmental-dynamics simulation strategy.

PubMed

Liu, Hui; Hu, Dawei; Dong, Chen; Fu, Yuming; Liu, Guanghui; Qin, Youcai; Sun, Yi; Liu, Dianlei; Li, Lei; Liu, Hong

2017-08-01

There is much uncertainty about the risks of seed germination after repeated or protracted environmental low-dose ionizing radiation exposure. The purpose of this study is to explore the influence mechanism of low-dose ionizing radiation on wheat seed germination using a model linking physiological characteristics and developmental-dynamics simulation. A low-dose ionizing radiation environment simulator was built to investigate wheat (Triticum aestivum L.) seeds germination process and then a kinetic model expressing the relationship between wheat seed germination dynamics and low-dose ionizing radiation intensity variations was developed by experimental data, plant physiology, relevant hypotheses and system dynamics, and sufficiently validated and accredited by computer simulation. Germination percentages were showing no differences in response to different dose rates. However, root and shoot lengths were reduced significantly. Plasma governing equations were set up and the finite element analysis demonstrated H 2 O, CO 2 , O 2 as well as the seed physiological responses to the low-dose ionizing radiation. The kinetic model was highly valid, and simultaneously the related influence mechanism of low-dose ionizing radiation on wheat seed germination proposed in the modeling process was also adequately verified. Collectively these data demonstrate that low-dose ionizing radiation has an important effect on absorbing water, consuming O 2 and releasing CO 2 , which means the risk for embryo and endosperm development was higher. Copyright © 2017 Elsevier Ltd. All rights reserved.

TIME DEPENDENT NONEQUILIBRIUM IONIZATION OF TRANSITION REGION LINES OBSERVED WITH IRIS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martínez-Sykora, Juan; Pontieu, Bart De; Hansteen, Viggo H.

The properties of nonstatistical equilibrium ionization of silicon and oxygen ions are analyzed in this work. We focus on five solar targets (quiet Sun; coronal hole; plage; quiescent active region, AR; and flaring AR) as observed with the Interface Region Imaging Spectrograph (IRIS). IRIS is best suited for this work owing to the high cadence (up to 0.5 s), high spatial resolution (up to 0.″32), and high signal-to-noise ratios for O iv λ1401 and Si iv λ1402. We find that the observed intensity ratio between lines of three times ionized silicon and oxygen ions depends on their total intensity and that this correlationmore » varies depending on the region observed (quiet Sun, coronal holes, plage, or active regions) and on the specific observational objects present (spicules, dynamic loops, jets, microflares, or umbra). In order to interpret the observations, we compare them with synthetic profiles taken from 2D self-consistent radiative MHD simulations of the solar atmosphere, where the statistical equilibrium or nonequilibrium treatment of silicon and oxygen is applied. These synthetic observations show vaguely similar correlations to those in the observations, i.e., between the intensity ratios and their intensities, but only in the nonequilibrium case do we find that (some of) the observations can be reproduced. We conclude that these lines are formed out of statistical equilibrium. We use our time-dependent nonequilibrium ionization simulations to describe the physical mechanisms behind these observed properties.« less

Magnetic reconnection in the low solar chromosphere with a more realistic radiative cooling model

NASA Astrophysics Data System (ADS)

Ni, Lei; Lukin, Vyacheslav S.; Murphy, Nicholas A.; Lin, Jun

2018-04-01

Magnetic reconnection is the most likely mechanism responsible for the high temperature events that are observed in strongly magnetized locations around the temperature minimum in the low solar chromosphere. This work improves upon our previous work [Ni et al., Astrophys. J. 852, 95 (2018)] by using a more realistic radiative cooling model computed from the OPACITY project and the CHIANTI database. We find that the rate of ionization of the neutral component of the plasma is still faster than recombination within the current sheet region. For low β plasmas, the ionized and neutral fluid flows are well-coupled throughout the reconnection region resembling the single-fluid Sweet-Parker model dynamics. Decoupling of the ion and neutral inflows appears in the higher β case with β0=1.46 , which leads to a reconnection rate about three times faster than the rate predicted by the Sweet-Parker model. In all cases, the plasma temperature increases with time inside the current sheet, and the maximum value is above 2 ×104 K when the reconnection magnetic field strength is greater than 500 G. While the more realistic radiative cooling model does not result in qualitative changes of the characteristics of magnetic reconnection, it is necessary for studying the variations of the plasma temperature and ionization fraction inside current sheets in strongly magnetized regions of the low solar atmosphere. It is also important for studying energy conversion during the magnetic reconnection process when the hydrogen-dominated plasma approaches full ionization.

Recommended direct simulation Monte Carlo collision model parameters for modeling ionized air transport processes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swaminathan-Gopalan, Krishnan; Stephani, Kelly A., E-mail: ksteph@illinois.edu

2016-02-15

A systematic approach for calibrating the direct simulation Monte Carlo (DSMC) collision model parameters to achieve consistency in the transport processes is presented. The DSMC collision cross section model parameters are calibrated for high temperature atmospheric conditions by matching the collision integrals from DSMC against ab initio based collision integrals that are currently employed in the Langley Aerothermodynamic Upwind Relaxation Algorithm (LAURA) and Data Parallel Line Relaxation (DPLR) high temperature computational fluid dynamics solvers. The DSMC parameter values are computed for the widely used Variable Hard Sphere (VHS) and the Variable Soft Sphere (VSS) models using the collision-specific pairing approach.more » The recommended best-fit VHS/VSS parameter values are provided over a temperature range of 1000-20 000 K for a thirteen-species ionized air mixture. Use of the VSS model is necessary to achieve consistency in transport processes of ionized gases. The agreement of the VSS model transport properties with the transport properties as determined by the ab initio collision integral fits was found to be within 6% in the entire temperature range, regardless of the composition of the mixture. The recommended model parameter values can be readily applied to any gas mixture involving binary collisional interactions between the chemical species presented for the specified temperature range.« less

Effects of Lightning in the Upper Atmosphere

NASA Astrophysics Data System (ADS)

Sentman, Davis D.; Pasko, Victor P.; Morrill, Jeff S.

2010-02-01

AGU Chapman Conference on Effects of Thunderstorms and Lightning in the Upper Atmosphere; University Park, Pennsylvania, 10-14 May 2009; The serendipitous observation in 1989 of electrical discharge in the high atmosphere induced by thundercloud lightning launched a new field of geophysical investigation. From this single unexpected observation sprang a vigorous and fertile new research field that simultaneously encompasses geophysical disciplines that are normally pursued independently, such as meteorology and lightning, plasma and gas discharge physics, atmospheric chemistry, ionospheric physics, and energetic particle physics. Transient electrical discharge in the upper atmosphere spans the full range of altitudes between the tropopause and the ionosphere and takes a variety of forms that carry the whimsical names red sprites, blue jets, gigantic jets, elves (emissions of light and very low frequency perturbations from electromagnetic pulse sources), and sprite halos, collectively known as transient luminous events (TLEs). To date, TLEs have been observed from ground and airborne or spaceborne platforms above thunderstorm systems worldwide, and radio observations made concomitantly with optical observations have shown that they are produced by the transient far fields of thundercloud lightning. TLEs appear to be large-scale (tens of kilometers in dimension), upper atmospheric versions of conventional gas discharge akin to weakly ionized, collision-dominated systems found in laboratory discharge devices (millimeter-centimeter dimensions), with characteristic energies of a few electron volts. The dominant physical processes have been identified as described by the familiar kinetic theory of the photochemistry of the upper atmosphere, but with electric field-driven electron impact ionization playing the role of photolysis or energetic precipitating particle-induced ionization.

Comparative study on ambient ionization methods for direct analysis of navel orange tissues by mass spectrometry.

PubMed

Zhang, Hua; Bibi, Aisha; Lu, Haiyan; Han, Jing; Chen, Huanwen

2017-08-01

It is of sustainable interest to improve the sensitivity and selectivity of the ionization process, especially for direct analysis of complex samples without matrix separation. Herein, four ambient ionization methods including desorption atmospheric pressure chemical ionization (DAPCI), heat-assisted desorption atmospheric pressure chemical ionization (heat-assisted DAPCI), microwave plasma torch (MPT) and internal extractive electrospray ionization (iEESI) were employed for comparative analysis of the navel orange tissue samples by mass spectrometry. The volatile organic compounds (e.g. ethanol, vanillin, leaf alcohol and jasmine lactone) were successfully detected by non-heat-assisted DAPCI-MS, while semi-volatile organic compounds (e.g. 1-nonanol and ethyl nonanoate) together with low abundance of non-volatile organic compounds (e.g. sinensetin and nobiletin) were obtained by heat-assisted DAPCI-MS. Typical nonvolatile organic compounds [e.g. 5-(hydroxymethyl)furfural and glucosan] were sensitively detected with MPT-MS. Compounds of high polarity (e.g. amino acids, alkaloids and sugars) were easily profiled with iEESI-MS. Our data showed that more analytes could be detected when more energy was delivered for the desorption ionization purpose; however, heat-sensitive analytes would not be detected once the energy input exceeded the dissociation barriers of the analytes. For the later cases, soft ionization methods such as iEESI were recommended to sensitively profile the bioanalytes of high polarity. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

Recollision induced excitation-ionization with counter-rotating two-color circularly polarized laser field

NASA Astrophysics Data System (ADS)

Ben, Shuai; Guo, Pei-Ying; Pan, Xue-Fei; Xu, Tong-Tong; Song, Kai-Li; Liu, Xue-Shen

2017-07-01

Nonsequential double ionization of Ar by a counter-rotating two-color circularly polarized laser field is theoretically investigated. At the combined intensity in the "knee" structure range, the double ionization occurs mainly through recollision induced excitation followed by subsequent ionization of Ar+∗ . By tracing the history of the recollision trajectories, we explain how the relative intensity ratio of the two colors controls the correlated electron dynamics and optimizes the ionization yields. The major channels contributing to enhancing the double ionization are through the elliptical trajectories with smaller travel time but not through the triangle shape or the other long cycle trajectories. Furthermore, the correlated electron dynamics could be limited to the attosecond time scale by adjusting the relative intensity ratio. Finally, the double ionization from doubly excited complex at low laser intensity is qualitatively discussed.

Propagation of intense short laser pulses in the atmosphere.

PubMed

Sprangle, P; Peñano, J R; Hafizi, B

2002-10-01

The propagation of short, intense laser pulses in the atmosphere is investigated theoretically and numerically. A set of three-dimensional (3D), nonlinear propagation equations is derived, which includes the effects of dispersion, nonlinear self-focusing, stimulated molecular Raman scattering, multiphoton and tunneling ionization, energy depletion due to ionization, relativistic focusing, and ponderomotively excited plasma wakefields. The instantaneous frequency spread along a laser pulse in air, which develops due to various nonlinear effects, is analyzed and discussed. Coupled equations for the power, spot size, and electron density are derived for an intense ionizing laser pulse. From these equations we obtain an equilibrium for a single optical-plasma filament, which involves a balancing between diffraction, nonlinear self-focusing, and plasma defocusing. The equilibrium is shown to require a specific distribution of power along the filament. It is found that in the presence of ionization a self-guided optical filament is not realizable. A method for generating a remote spark in the atmosphere is proposed, which utilizes the dispersive and nonlinear properties of air to cause a low-intensity chirped laser pulse to compress both longitudinally and transversely. For optimally chosen parameters, we find that the transverse and longitudinal focal lengths can be made to coincide, resulting in rapid intensity increase, ionization, and white light generation in a localized region far from the source. Coupled equations for the laser spot size and pulse duration are derived, which can describe the focusing and compression process in the low-intensity regime. More general examples involving beam focusing, compression, ionization, and white light generation near the focal region are studied by numerically solving the full set of 3D, nonlinear propagation equations.

Epicyclic helical channels for parametric resonance ionization cooling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Johson, Rolland Paul; Derbenev, Yaroslav

Proposed next-generation muon colliders will require major technical advances to achieve rapid muon beam cooling requirements. Parametric-resonance Ionization Cooling (PIC) is proposed as the final 6D cooling stage of a high-luminosity muon collider. In PIC, a half-integer parametric resonance causes strong focusing of a muon beam at appropriately placed energy absorbers while ionization cooling limits the beam’s angular spread. Combining muon ionization cooling with parametric resonant dynamics in this way should then allow much smaller final transverse muon beam sizes than conventional ionization cooling alone. One of the PIC challenges is compensation of beam aberrations over a sufficiently wide parametermore » range while maintaining the dynamical stability with correlated behavior of the horizontal and vertical betatron motion and dispersion. We explore use of a coupling resonance to reduce the dimensionality of the problem and to shift the dynamics away from non-linear resonances. PIC simulations are presented.« less

Atmospheric-pressure ionization and fragmentation of peptides by solution-cathode glow discharge† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c6sc02032a Click here for additional data file.

PubMed Central

Schwartz, Andrew J.; Walton, Courtney L.; Williams, Kelsey L.; Hieftje, Gary M.

2016-01-01

Modern “-omics” (e.g., proteomics, glycomics, metabolomics, etc.) analyses rely heavily on electrospray ionization and tandem mass spectrometry to determine the structural identity of target species. Unfortunately, these methods are limited to specialized mass spectrometry instrumentation. Here, a novel approach is described that enables ionization and controlled, tunable fragmentation of peptides at atmospheric pressure. In the new source, a direct-current plasma is sustained between a tapered metal rod and a flowing sample-containing solution. As the liquid stream contacts the electrical discharge, peptides from the solution are volatilized, ionized, and fragmented. At high discharge currents (e.g., 70 mA), electrospray-like spectra are observed, dominated by singly and doubly protonated molecular ions. At lower currents (35 mA), many peptides exhibit extensive fragmentation, with a-, b-, c-, x-, and y-type ion series present as well as complex fragments, such as d-type ions, not previously observed with atmospheric-pressure dissociation. Though the mechanism of fragmentation is currently unclear, observations indicate it could result from the interaction of peptides with gas-phase radicals or ultraviolet radiation generated within the plasma. PMID:28451101

Computational Model of D-Region Ion Production Caused by Energetic Electron Precipitations Based on General Monte Carlo Transport Calculations

NASA Astrophysics Data System (ADS)

Kouznetsov, A.; Cully, C. M.

2017-12-01

During enhanced magnetic activities, large ejections of energetic electrons from radiation belts are deposited in the upper polar atmosphere where they play important roles in its physical and chemical processes, including VLF signals subionospheric propagation. Electron deposition can affect D-Region ionization, which are estimated based on ionization rates derived from energy depositions. We present a model of D-region ion production caused by an arbitrary (in energy and pitch angle) distribution of fast (10 keV - 1 MeV) electrons. The model relies on a set of pre-calculated results obtained using a general Monte Carlo approach with the latest version of the MCNP6 (Monte Carlo N-Particle) code for the explicit electron tracking in magnetic fields. By expressing those results using the ionization yield functions, the pre-calculated results are extended to cover arbitrary magnetic field inclinations and atmospheric density profiles, allowing ionization rate altitude profile computations in the range of 20 and 200 km at any geographic point of interest and date/time by adopting results from an external atmospheric density model (e.g. NRLMSISE-00). The pre-calculated MCNP6 results are stored in a CDF (Common Data Format) file, and IDL routines library is written to provide an end-user interface to the model.

Application of dynamic displacement current for diagnostics of subnanosecond breakdowns in an inhomogeneous electric field

NASA Astrophysics Data System (ADS)

Shao, Tao; Tarasenko, Victor F.; Zhang, Cheng; Burachenko, Alexandr G.; Rybka, Dmitry V.; Kostyrya, Igor'D.; Lomaev, Mikhail I.; Baksht, Evgeni Kh.; Yan, Ping

2013-05-01

The breakdown of different air gaps at high overvoltages in an inhomogeneous electric field was investigated with a time resolution of up to 100 ps. Dynamic displacement current was used for diagnostics of ionization processes between the ionization wave front and a plane anode. It is demonstrated that during the generation of a supershort avalanche electron beam (SAEB) with amplitudes of ˜10 A and more, conductivity in the air gaps at the breakdown stage is ensured by the ionization wave, whose front propagates from the electrode of small curvature radius, and by the dynamic displacement current between the ionization wave front and the plane electrode. The amplitude of the dynamic displacement current measured by a current shunt is 100 times greater than the SAEB. It is shown that with small gaps and with a large cathode diameter, the amplitude of the dynamic displacement current during a subnanosecond rise time of applied pulse voltage can be higher than 4 kA.

Ionization-potential depression and dynamical structure factor in dense plasmas

NASA Astrophysics Data System (ADS)

Lin, Chengliang; Röpke, Gerd; Kraeft, Wolf-Dietrich; Reinholz, Heidi

2017-07-01

The properties of a bound electron system immersed in a plasma environment are strongly modified by the surrounding plasma. The modification of an essential quantity, the ionization energy, is described by the electronic and ionic self-energies, including dynamical screening within the framework of the quantum statistical theory. Introducing the ionic dynamical structure factor as the indicator for the ionic microfield, we demonstrate that ionic correlations and fluctuations play a critical role in determining the ionization potential depression. This is, in particular, true for mixtures of different ions with large mass and charge asymmetry. The ionization potential depression is calculated for dense aluminum plasmas as well as for a CH plasma and compared to the experimental data and more phenomenological approaches used so far.

Atmospheric Ionizing Radiation (AIR) ER-2 Preflight Analysis

NASA Technical Reports Server (NTRS)

Tai, Hsiang; Wilson, John W.; Maiden, D. L.

1998-01-01

Atmospheric ionizing radiation (AIR) produces chemically active radicals in biological tissues that alter the cell function or result in cell death. The AIR ER-2 flight measurements will enable scientists to study the radiation risk associated with the high-altitude operation of a commercial supersonic transport. The ER-2 radiation measurement flights will follow predetermined, carefully chosen courses to provide an appropriate database matrix which will enable the evaluation of predictive modeling techniques. Explicit scientific results such as dose rate, dose equivalent rate, magnetic cutoff, neutron flux, and air ionization rate associated with those flights are predicted by using the AIR model. Through these flight experiments, we will further increase our knowledge and understanding of the AIR environment and our ability to assess the risk from the associated hazard.

The unexpected formation of [M - H]+ species during MALDI and dopant-free APPI MS analysis of novel antineoplastic curcumin analogues.

PubMed

Awad, H; Stoudemayer, M J; Usher, L; Amster, I J; Cohen, A; Das, U; Whittal, R M; Dimmock, J; El-Aneed, A

2014-11-01

Unusual ionization behavior was observed with novel antineoplastic curcumin analogues during the positive ion mode of matrix-assisted laser desorption ionization (MALDI) and dopant-free atmospheric pressure photoionization (APPI). The tested compounds produced an unusual significant peak designated as [M - H](+) ion along with the expected [M + H](+) species. In contrast, electrospray ionization, atmospheric pressure chemical ionization and the dopant-mediated APPI (dopant-APPI) showed only the expected [M + H](+) peak. The [M - H](+) ion was detected with all evaluated curcumin analogues including phosphoramidates, secondary amines, amides and mixed amines/amides. Our experiments revealed that photon energy triggers the ionization of the curcumin analogues even in the absence of any ionization enhancer such as matrix, solvent or dopant. The possible mechanisms for the formation of both [M - H](+) and [M + H](+) ions are discussed in this paper. In particular, three proposed mechanisms for the formation of [M - H](+) were evaluated. The first mechanism involves the loss of H2 from the protonated [M + H](+) species. The other two mechanisms include hydrogen transfer from the analyte radical cation or hydride abstraction from the neutral analyte molecule. Copyright © 2014 John Wiley & Sons, Ltd.

Formation of Metal-Adducted Analyte Ions by Flame-Induced Atmospheric Pressure Chemical Ionization Mass Spectrometry.

PubMed

Cheng, Sy-Chyi; Wang, Chin-Hsiung; Shiea, Jentaie

2016-05-17

A flame-induced atmospheric pressure chemical ionization (FAPCI) source, consisting of a miniflame, nebulizer, and heated tube, was developed to ionize analytes. The ionization was performed by reacting analytes with a charged species generated in a flame. A stainless steel needle deposited with saturated alkali chloride solution was introduced into the mini oxyacetylene flame to generate alkali ions, which were reacted with analytes (M) generated in a heated nebulizer. The alkali-adducted 18-crown-6 ether ions, including (M + Li)(+), (M + Na)(+), (M + K)(+), (M + Rb)(+), and (M + Cs)(+), were successfully detected on the FAPCI mass spectra when the corresponding alkali chloride solutions were separately introduced to the flame. When an alkali chloride mixture was introduced, all alkali-adducted analyte ions were simultaneously detected. Their intensity order was as follows: (M + Cs)(+) > (M + Rb)(+) > (M + K)(+) > (M + Na)(+) > (M + Li)(+), and this trend agreed with the lattice energies of alkali chlorides. Besides alkali ions, other transition metal ions such as Ni(+), Cu(+), and Ag(+) were generated in a flame for analyte ionization. Other than metal ions, the reactive species generated in the fossil fuel flame could also be used to ionize analytes, which formed protonated analyte ions (M + H)(+) in positive ion mode and deprotonated analyte ions (M - H)(-) in negative ion mode.

Electron Impact Ionization: A New Parameterization for 100 eV to 1 MeV Electrons

NASA Technical Reports Server (NTRS)

Fang, Xiaohua; Randall, Cora E.; Lummerzheim, Dirk; Solomon, Stanley C.; Mills, Michael J.; Marsh, Daniel; Jackman, Charles H.; Wang, Wenbin; Lu, Gang

2008-01-01

Low, medium and high energy electrons can penetrate to the thermosphere (90-400 km; 55-240 miles) and mesosphere (50-90 km; 30-55 miles). These precipitating electrons ionize that region of the atmosphere, creating positively charged atoms and molecules and knocking off other negatively charged electrons. The precipitating electrons also create nitrogen-containing compounds along with other constituents. Since the electron precipitation amounts change within minutes, it is necessary to have a rapid method of computing the ionization and production of nitrogen-containing compounds for inclusion in computationally-demanding global models. A new methodology has been developed, which has parameterized a more detailed model computation of the ionizing impact of precipitating electrons over the very large range of 100 eV up to 1,000,000 eV. This new parameterization method is more accurate than a previous parameterization scheme, when compared with the more detailed model computation. Global models at the National Center for Atmospheric Research will use this new parameterization method in the near future.

Continuous Flow Atmospheric Pressure Laser Desorption/Ionization Using a 6–7-µm-Band Mid-Infrared Tunable Laser for Biomolecular Mass Spectrometry

PubMed Central

Hiraguchi, Ryuji; Hazama, Hisanao; Senoo, Kenichirou; Yahata, Yukinori; Masuda, Katsuyoshi; Awazu, Kunio

2014-01-01

A continuous flow atmospheric pressure laser desorption/ionization technique using a porous stainless steel probe and a 6–7-µm-band mid-infrared tunable laser was developed. This ion source is capable of direct ionization from a continuous flow with a high temporal stability. The 6–7-µm wavelength region corresponds to the characteristic absorption bands of various molecular vibration modes, including O–H, C=O, CH3 and C–N bonds. Consequently, many organic compounds and solvents, including water, have characteristic absorption peaks in this region. This ion source requires no additional matrix, and utilizes water or acetonitrile as the solvent matrix at several absorption peak wavelengths (6.05 and 7.27 µm, respectively). The distribution of multiply-charged peptide ions is extremely sensitive to the temperature of the heated capillary, which is the inlet of the mass spectrometer. This ionization technique has potential for the interface of liquid chromatography/mass spectrometry (LC/MS). PMID:24937686

Alfvén ionization in an MHD-gas interactions code

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wilson, A. D.; Diver, D. A.

A numerical model of partially ionized plasmas is developed in order to capture their evolving ionization fractions as a result of Alfvén ionization (AI). The mechanism of, and the parameter regime necessary for, AI is discussed and an expression for the AI rate based on fluid parameters, from a gas-MHD model, is derived. This AI term is added to an existing MHD-gas interactions' code, and the result is a linear, 2D, two-fluid model that includes momentum transfer between charged and neutral species as well as an ionization rate that depends on the velocity fields of both fluids. The dynamics ofmore » waves propagating through such a partially ionized plasma are investigated, and it is found that AI has a significant influence on the fluid dynamics as well as both the local and global ionization fraction.« less

Luminous phenomena and electromagnetic VHF wave emission originated from earthquake-related radon exhalation

NASA Astrophysics Data System (ADS)

Seki, A.; Tobo, I.; Omori, Y.; Muto, J.; Nagahama, H.

2013-12-01

Anomalous luminous phenomena and electromagnetic wave emission before or during earthquakes have been reported (e.g., the 1965 Matsushiro earthquake swarm). However, their mechanism is still unsolved, in spite of many models for these phenomena. Here, we propose a new model about luminous phenomena and electromagnetic wave emission during earthquake by focusing on atmospheric radon (Rn-222) and its daughter nuclides (Po-218 and Po-214). Rn-222, Po-218 and Po-214 are alpha emitters, and these alpha particles ionize atmospheric molecules. A light emission phenomenon, called 'the air luminescence', is caused by de-excitation of the ionized molecules of atmospheric nitrogen due to electron impact ionization from alpha particles. The de-excitation is from the second positive system of neutral nitrogen molecules and the first negative system of nitrogen molecule ion. Wavelengths of lights by these transitions include the visible light wavelength. So based on this mechanism, we proposed a new luminous phenomenon model before or during earthquake: 1. The concentration of atmospheric radon and its daughter nuclides increase anomalously before or during earthquakes, 2. Nitrogen molecules and their ions are excited by alpha particles emitted from Rn-222, Po-218 and Po-214, and air luminescence is generated by their de-excitation. Similarly, electromagnetic VHF wave emission can be explained by ionizing effect of radon and its daughter nuclides. Boyarchuk et al. (2005) proposed a model that electromagnetic VHF wave emission is originated when excited state of neutral clusters changes. Radon gas ionizes atmosphere and forms positively and negatively charged heavy particles. The process of ion hydration in ordinary air can be determined by the formation of complex chemically active structures of the various types of ion radicals. As a result of the association of such hydration radical ions, a neutral cluster, which is dipole quasi-molecules, is formed. A neutral cluster's rotation-rotation transition causes electromagnetic VHF wave emission. We also discuss a possibility of electromagnetic VHF wave emission from excitation of polyatomic molecules by alpha particles from Rn-222 and its daughter nuclides, similar to air luminescence by excitation of nitrogen molecule in the viewpoint of electromagnetic radiation in quantum theory.

Excited level populations and excitation kinetics of nonequilibrium ionizing argon discharge plasma of atmospheric pressure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Akatsuka, Hiroshi

2009-04-15

Population densities of excited states of argon atoms are theoretically examined for ionizing argon plasma in a state of nonequilibrium under atmospheric pressure from the viewpoint of elementary processes with collisional radiative model. The dependence of excited state populations on the electron and gas temperatures is discussed. Two electron density regimes are found, which are distinguished by the population and depopulation mechanisms for the excited states in problem. When the electron impact excitation frequency for the population or depopulation is lower than the atomic impact one, the electron density of the plasma is considered as low to estimate the populationmore » and depopulation processes. Some remarkable characteristics of population and depopulation mechanisms are found for the low electron density atmospheric plasma, where thermal relaxation by atomic collisions becomes the predominant process within the group of close-energy states in the ionizing plasma of atmospheric pressure, and the excitation temperature is almost the same as the gas temperature. In addition to the collisional relaxation by argon atoms, electron impact excitation from the ground state is also an essential population mechanism. The ratios of population density of the levels pairs, between which exists a large energy gap, include information on the electron collisional kinetics. For high electron density, the effect of atomic collisional relaxation becomes weak. For this case, the excitation mechanism is explained as electron impact ladderlike excitation similar to low-pressure ionizing plasma, since the electron collision becomes the dominant process for the population and depopulation kinetics.« less

Ionization pattern obtained in electrospray ionization or atmospheric pressure chemical ionization interfaces for authorized antidepressants in Romania

NASA Astrophysics Data System (ADS)

Grecu, Iulia; Ionicǎ, Mihai; Vlǎdescu, Marian; Truţǎ, Elena; Sultan, Carmen; Viscol, Oana; Horhotǎ, Luminiţa; Radu, Simona

2016-12-01

Antidepressants were found in 1950. In the 1990s there was a new generation of antidepressants. They act on the level of certain neurotransmitters extrasinpatic by its growth. After their mode of action antidepressants may be: SSRIs (Selective Serotonin Reuptake Inhibitors); (Serotonin-Norepinephrine Reuptake Inhibitors); SARIs (Serotonin Antagonist Reuptake Inhibitors); NRIs (Norepinephrine Reuptake Inhibitors); NDRIs (Norepinephrine-Dopamine Reuptake Inhibitors) NDRAs (Norepinephrine-Dopamine Releasing Agents); TCAs (Tricyclic Antidepressants); TeCAs (Tetracyclic Antidepressants); MAOIs (Monoamine Oxidase Inhibitors); agonist receptor 5-HT1A (5- hydroxytryptamine); antagonist receptor 5-HT2; SSREs (Selective Serotonin Reuptake Enhancers) and Sigma agonist receptor. To determine the presence of antidepressants in biological products, it has been used a system HPLC-MS (High Performance Liquid Chromatography - Mass Spectrometry) Varian 12001. The system is equipped with APCI (Atmospheric Pressure Chemical Ionization) or ESI (ElectroSpray Ionization) interface. To find antidepressants in unknown samples is necessary to recognize them after mass spectrum. Because the mass spectrum it is dependent on obtaining private parameters work of HPLC-MS system, and control interfaces, the mass spectra library was filled with the mass spectra of all approved antidepressants in Romania. The paper shows the mass spectra obtained in the HPLCMS system.

Confluence or independence of microwave plasma bullets in atmospheric argon plasma jet plumes

NASA Astrophysics Data System (ADS)

Li, Ping; Chen, Zhaoquan; Mu, Haibao; Xu, Guimin; Yao, Congwei; Sun, Anbang; Zhou, Yuming; Zhang, Guanjun

2018-03-01

Plasma bullet is the formation and propagation of a guided ionization wave (streamer), normally generated in atmospheric pressure plasma jet (APPJ). In most cases, only an ionization front produces in a dielectric tube. The present study shows that two or three ionization fronts can be generated in a single quartz tube by using a microwave coaxial resonator. The argon APPJ plumes with a maximum length of 170 mm can be driven by continuous microwaves or microwave pulses. When the input power is higher than 90 W, two or three ionization fronts propagate independently at first; thereafter, they confluence to form a central plasma jet plume. On the other hand, the plasma bullets move independently as the lower input power is applied. For pulsed microwave discharges, the discharge images captured by a fast camera show the ionization process in detail. Another interesting finding is that the strongest lightening plasma jet plumes always appear at the shrinking phase. Both the discharge images and electromagnetic simulations suggest that the confluence or independent propagation of plasma bullets is resonantly excited by the local enhanced electric fields, in terms of wave modes of traveling surface plasmon polaritons.

Physical bases of the generation of short-term earthquake precursors: A complex model of ionization-induced geophysical processes in the lithosphere-atmosphere-ionosphere-magnetosphere system

NASA Astrophysics Data System (ADS)

Pulinets, S. A.; Ouzounov, D. P.; Karelin, A. V.; Davidenko, D. V.

2015-07-01

This paper describes the current understanding of the interaction between geospheres from a complex set of physical and chemical processes under the influence of ionization. The sources of ionization involve the Earth's natural radioactivity and its intensification before earthquakes in seismically active regions, anthropogenic radioactivity caused by nuclear weapon testing and accidents in nuclear power plants and radioactive waste storage, the impact of galactic and solar cosmic rays, and active geophysical experiments using artificial ionization equipment. This approach treats the environment as an open complex system with dissipation, where inherent processes can be considered in the framework of the synergistic approach. We demonstrate the synergy between the evolution of thermal and electromagnetic anomalies in the Earth's atmosphere, ionosphere, and magnetosphere. This makes it possible to determine the direction of the interaction process, which is especially important in applications related to short-term earthquake prediction. That is why the emphasis in this study is on the processes proceeding the final stage of earthquake preparation; the effects of other ionization sources are used to demonstrate that the model is versatile and broadly applicable in geophysics.

Solar modulation of atmospheric electrification through variation of the conductivity over thunderstorms

NASA Technical Reports Server (NTRS)

Markson, R.

1975-01-01

It is suggested that variations of the current in the global atmospheric electrical circuit can be produced through regulation of the resistance between the tops of thunderclouds and the ionosphere. Long- and short-term changes in the conductivity of this region occur due to changes in the ionization rate resulting from solar activity. Previous suggestions that the phenomena might be due to conductivity variations in the fair weather part of the world or an influx of space charge to the upper atmosphere are discussed and considered unlikely. It might be possible to test the proposed mechanism by measuring the temporal variation of the ionospheric potential during distributed solar periods. Another approach would be to measure simultaneously the variation in ionization rate and electric current over thunderstorms. Several ways in which changes in atmospheric electrification might influence other meteorological phenomena are mentioned.

Interaction of Titan's ionosphere with Saturn's magnetosphere.

PubMed

Coates, Andrew J

2009-02-28

Titan is the only Moon in the Solar System with a significant permanent atmosphere. Within this nitrogen-methane atmosphere, an ionosphere forms. Titan has no significant magnetic dipole moment, and is usually located inside Saturn's magnetosphere. Atmospheric particles are ionized both by sunlight and by particles from Saturn's magnetosphere, mainly electrons, which reach the top of the atmosphere. So far, the Cassini spacecraft has made over 45 close flybys of Titan, allowing measurements in the ionosphere and the surrounding magnetosphere under different conditions. Here we review how Titan's ionosphere and Saturn's magnetosphere interact, using measurements from Cassini low-energy particle detectors. In particular, we discuss ionization processes and ionospheric photoelectrons, including their effect on ion escape from the ionosphere. We also discuss one of the unexpected discoveries in Titan's ionosphere, the existence of extremely heavy negative ions up to 10000amu at 950km altitude.

First Results From the Ionospheric Extension of WACCM-X During the Deep Solar Minimum Year of 2008

NASA Astrophysics Data System (ADS)

Liu, Jing; Liu, Hanli; Wang, Wenbin; Burns, Alan G.; Wu, Qian; Gan, Quan; Solomon, Stanley C.; Marsh, Daniel R.; Qian, Liying; Lu, Gang; Pedatella, Nicholas M.; McInerney, Joe M.; Russell, James M.; Schreiner, William S.

2018-02-01

New ionosphere and electrodynamics modules have been incorporated in the thermosphere and ionosphere eXtension of the Whole Atmosphere Community Climate Model (WACCM-X), in order to self-consistently simulate the coupled atmosphere-ionosphere system. The first specified dynamics WACCM-X v.2.0 results are compared with several data sets, and with the Thermosphere-Ionosphere-Electrodynamics General Circulation Model (TIE-GCM), during the deep solar minimum year. Comparisons with Thermosphere Ionosphere Mesosphere Energetics and Dynamics satellite of temperature and zonal wind in the lower thermosphere show that WACCM-X reproduces the seasonal variability of tides remarkably well, including the migrating diurnal and semidiurnal components and the nonmigrating diurnal eastward propagating zonal wavenumber 3 component. There is overall agreement between WACCM-X, TIE-GCM, and vertical drifts observed by the Communication/Navigation Outage Forecast System (C/NOFS) satellite over the magnetic equator, but apparent discrepancies also exist. Both model results are dominated by diurnal variations, while C/NOFS observed vertical plasma drifts exhibit strong temporal variations. The climatological features of ionospheric peak densities and heights (NmF2 and hmF2) from WACCM-X are in general agreement with the results derived from Constellation Observing System for Meteorology, Ionosphere and Climate (COSMIC) data, although the WACCM-X predicted NmF2 values are smaller, and the equatorial ionization anomaly crests are closer to the magnetic equator compared to COSMIC and ionosonde observations. This may result from the excessive mixing in the lower thermosphere due to the gravity wave parameterization. These data-model comparisons demonstrate that WACCM-X can capture the dynamic behavior of the coupled atmosphere and ionosphere in a climatological sense.

Texes Observations of M Supergiants: Dynamics and Thermodynamics of Wind Acceleration

NASA Astrophysics Data System (ADS)

Harper, Graham M.; Richter, Matthew J.; Ryde, Nils; Brown, Alexander; Brown, Joanna; Greathouse, Thomas K.; Strong, Shadrian

2009-08-01

We have detected [Fe II] 17.94 μm and 24.52 μm emission from a sample of M supergiants (μ Cep, α Sco, α Ori, CE Tau, AD Per, and α Her) using the Texas Echelon Cross Echelle Spectrograph on NASA's Infrared Telescope Facility. These low opacity emission lines are resolved at R sime 50, 000 and provide new diagnostics of the dynamics and thermodynamics of the stellar wind acceleration zone. The [Fe II] lines, from the first excited term (a 4 F), are sensitive to the warm plasma where energy is deposited into the extended atmosphere to form the chromosphere and wind outflow. These diagnostics complement previous Kuiper Airborne Observatory and Infrared Space Observatory observations which were sensitive to the cooler and more extended circumstellar envelopes. The turbulent velocities of V turb sime 12-13 km s-1 observed in the [Fe II] a 4 F forbidden lines are found to be a common property of our sample, and are less than that derived from the hotter chromospheric C II] 2325 Å lines observed in α Ori, where V turb sime 17-19 km s-1. For the first time, we have dynamically resolved the motions of the dominant cool atmospheric component discovered in α Ori from multiwavelength radio interferometry by Lim et al. Surprisingly, the emission centroids are quite Gaussian and at rest with respect to the M supergiants. These constraints combined with model calculations of the infrared emission line fluxes for α Ori imply that the warm material has a low outflow velocity and is located close to the star. We have also detected narrow [Fe I] 24.04 μm emission that confirms Fe II is the dominant ionization state in α Ori's extended atmosphere.

Collision-induced dissociation analysis of negative atmospheric ion adducts in atmospheric pressure corona discharge ionization mass spectrometry.

PubMed

Sekimoto, Kanako; Takayama, Mitsuo

2013-05-01

Collision-induced dissociation (CID) experiments were performed on atmospheric ion adducts [M + R](-) formed between various types of organic compounds M and atmospheric negative ions R(-) [such as O2(-), HCO3(-), COO(-)(COOH), NO2(-), NO3(-), and NO3(-)(HNO3)] in negative-ion mode atmospheric pressure corona discharge ionization (APCDI) mass spectrometry. All of the [M + R](-) adducts were fragmented to form deprotonated analytes [M - H](-) and/or atmospheric ions R(-), whose intensities in the CID spectra were dependent on the proton affinities of the [M - H](-) and R(-) fragments. Precursor ions [M + R](-) for which R(-) have higher proton affinities than [M - H](-) formed [M - H](-) as the dominant product. Furthermore, the CID of the adducts with HCO3(-) and NO3(-)(HNO3) led to other product ions such as [M + HO](-) and NO3(-), respectively. The fragmentation behavior of [M + R](-) for each R(-) observed was independent of analyte type (e.g., whether the analyte was aliphatic or aromatic, or possessed certain functional groups).

Estimated congener specific gas-phase atmospheric behavior and fractionation of perfluoroalkyl compounds: rates of reaction with atmospheric oxidants, air-water partitioning, and wet/dry deposition lifetimes.

PubMed

Rayne, Sierra; Forest, Kaya; Friesen, Ken J

2009-08-01

A quantitative structure-activity model has been validated for estimating congener specific gas-phase hydroxyl radical reaction rates for perfluoroalkyl sulfonic acids (PFSAs), carboxylic acids (PFCAs), aldehydes (PFAls) and dihydrates, fluorotelomer olefins (FTOls), alcohols (FTOHs), aldehydes (FTAls), and acids (FTAcs), and sulfonamides (SAs), sulfonamidoethanols (SEs), and sulfonamido carboxylic acids (SAAs), and their alkylated derivatives based on calculated semi-empirical PM6 method ionization potentials. Corresponding gas-phase reaction rates with nitrate radicals and ozone have also been estimated using the computationally derived ionization potentials. Henry's law constants for these classes of perfluorinated compounds also appear to be reasonably approximated by the SPARC software program, thereby allowing estimation of wet and dry atmospheric deposition rates. Both congener specific gas-phase atmospheric and air-water interface fractionation of these compounds is expected, complicating current source apportionment perspectives and necessitating integration of such differential partitioning influences into future multimedia models. The findings will allow development and refinement of more accurate and detailed local through global scale atmospheric models for the atmospheric fate of perfluoroalkyl compounds.

Dual parallel mass apectrometry (LC1/MS2 and LC2/MS2) for lipid and vitamin D analysis

USDA-ARS?s Scientific Manuscript database

Atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and electrospray ionization (ESI) MS are complementary techniques that provide different types of information for lipids such as triacylglycerols, phospholipids, and fat-soluble vitamins. Since no one technique is by itself idea...

Dual Parallel Mass Spectrometry (LC1/MS2 and LC2/MS2) for Lipid and Vitamin D Analysis

USDA-ARS?s Scientific Manuscript database

Atmospheric pressure chemical ionization (APCI) mass spectrometry (MS) and electrospray ionization (ESI) MS are complementary techniques that provide different types of information for lipids such as triacylglycerols (TAGs), phospholipids, and fat-soluble vitamins. Since no one technique is by itsel...

Sensitive determination of RDX, nitroso-RDX metabolites, and other munitions in ground water by solid-phase extraction and isotope dilution liquid chromatography-atmospheric pressure electro-spray [correction of chemical] ionization mass spectrometry.

PubMed

Cassada, D A; Monson, S J; Snow, D D; Spalding, R F

1999-06-04

Recent improvements in the LC-MS interface have increased the sensitivity and selectivity of this instrument in the analysis of polar and thermally-labile aqueous constituents. Determination of RDX, nitroso-RDX metabolites, and other munitions was enhanced using LC-MS with solid-phase extraction, 15N3-RDX internal standard, and electrospray ionization (ESI) in negative ion mode. ESI produced a five-fold increase in detector response over atmospheric pressure chemical ionization (APCI) for the nitramine compounds, while the more energetic APCI produced more than twenty times the ESI response for nitroaromatics. Method detection limits in ESI for nitramines varied from 0.03 microgram l-1 for MNX to 0.05 microgram l-1 for RDX.

Matrix Assisted Ionization Vacuum (MAIV), a New Ionization Method for Biological Materials Analysis Using Mass Spectrometry*

PubMed Central

Inutan, Ellen D.; Trimpin, Sarah

2013-01-01

The introduction of electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI) for the mass spectrometric analysis of peptides and proteins had a dramatic impact on biological science. We now report that a wide variety of compounds, including peptides, proteins, and protein complexes, are transported directly from a solid-state small molecule matrix to gas-phase ions when placed into the vacuum of a mass spectrometer without the use of high voltage, a laser, or added heat. This ionization process produces ions having charge states similar to ESI, making the method applicable for high performance mass spectrometers designed for atmospheric pressure ionization. We demonstrate highly sensitive ionization using intermediate pressure MALDI and modified ESI sources. This matrix and vacuum assisted soft ionization method is suitable for the direct surface analysis of biological materials, including tissue, via mass spectrometry. PMID:23242551

Ultrafast multiphoton ionization dynamics and control of NaK molecules

NASA Astrophysics Data System (ADS)

Davidsson, Jan; Hansson, Tony; Mukhtar, Emad

1998-12-01

The multiphoton ionization dynamics of NaK molecules is investigated experimentally using one-color pump-probe femtosecond spectroscopy at 795 nm and intermediate laser field strengths (about 10 GW/cm2). Both NaK+ and Na+ ions are detected as a function of pulse separation time, pulse intensities, and strong pulse-weak pulse order. To aid in the analysis, the potential energy curves of the two lowest electronic states of NaK+ and the electronic transition dipole moment between them are calculated by the GAUSSIAN94 UCIS method. Different ionization pathways are identified by Franck-Condon analysis, and vibrational dynamics in the A 1Σ+ and 3 1Π states, as well as in the ground state, is observed. Further, the existence of a highly excited (above the adiabatic ionization limit) neutral state of NaK is proposed. By changing the strong pulse-weak pulse order of the pulses, the ionization pathways for production of both ions can be varied and thus controlled.

Optical remote diagnostics of atmospheric propagating beams of ionizing radiation

DOEpatents

Karl JR., Robert R.

1990-03-06

Data is obtained for use in diagnosing the characteristics of a beam of ionizing radiation, such as charged particle beams, neutral particle beams, and gamma ray beams. In one embodiment the beam is emitted through the atmosphere and produces nitrogen fluorescence during passage through air. The nitrogen fluorescence is detected along the beam path to provide an intensity from which various beam characteristics can be calculated from known tabulations. Optical detecting equipment is preferably located orthogonal to the beam path at a distance effective to include the entire beam path in the equipment field of view.

Optical remote diagnostics of atmospheric propagating beams of ionizing radiation

DOEpatents

Karl, Jr., Robert R.

1990-01-01

Data is obtained for use in diagnosing the characteristics of a beam of ionizing radiation, such as charged particle beams, neutral particle beams, and gamma ray beams. In one embodiment the beam is emitted through the atmosphere and produces nitrogen fluorescence during passage through air. The nitrogen fluorescence is detected along the beam path to provide an intensity from which various beam characteristics can be calculated from known tabulations. Optical detecting equipment is preferably located orthogonal to the beam path at a distance effective to include the entire beam path in the equipment field of view.

Identification of astaxanthin diglucoside diesters from snow alga Chlamydomonas nivalis by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

PubMed

Rezanka, Tomás; Nedbalová, Linda; Sigler, Karel; Cepák, Vladislav

2008-01-01

A method is described for the identification of astaxanthin glucoside esters from snow alga Chlamydomonas nivalis by means of liquid chromatography-mass spectrometry with atmospheric pressure chemical ionization (LC-MS/APCI). The method is based on the use of preparative HPLC and subsequent identification of astaxanthin diglucoside diesters by microbore LC-MS/APCI. The combination of these two techniques was used to identify more than 100 molecular species. The astaxanthin diglucoside diester, i.e. (all-E)-[di-(6-O-oleoyl-beta-D-glucopyranosyloxy)]-astaxanthin, was also synthesized to unambiguously confirm its structure.

On the initiation of lightning in thunderclouds.

PubMed

Chilingarian, Ashot; Chilingaryan, Suren; Karapetyan, Tigran; Kozliner, Lev; Khanikyants, Yeghia; Hovsepyan, Gagik; Pokhsraryan, David; Soghomonyan, Suren

2017-05-02

The relationship of lightning and elementary particle fluxes in the thunderclouds is not fully understood to date. Using the particle beams (the so-called Thunderstorm Ground Enhancements - TGEs) as a probe we investigate the characteristics of the interrelated atmospheric processes. The well-known effect of the TGE dynamics is the abrupt termination of the particle flux by the lightning flash. With new precise electronics, we can see that particle flux decline occurred simultaneously with the rearranging of the charge centers in the cloud. The analysis of the TGE energy spectra before and after the lightning demonstrates that the high-energy part of the TGE energy spectra disappeared just after lightning. The decline of particle flux coincides on millisecond time scale with first atmospheric discharges and we can conclude that Relativistic Runaway Electron Avalanches (RREA) in the thundercloud assist initiation of the negative cloud to ground lightning. Thus, RREA can provide enough ionization to play a significant role in the unleashing of the lightning flash.

Understanding the Driver of Energetic Electron Precipitation Using Coordinated Multi-Satellite Measurements

NASA Astrophysics Data System (ADS)

Capannolo, L.; Li, W.; Ma, Q.

2017-12-01

Electron precipitation into the upper atmosphere is one of the important loss mechanisms in the Earth's inner magnetosphere. Various magnetospheric plasma waves (i.e., chorus, plasmaspheric hiss, electromagnetic ion cyclotron waves, etc.) play an important role in scattering energetic electrons into the loss cone, thus enhance ionization in the upper atmosphere and affect ring current and radiation belt dynamics. The present study evaluates conjunction events where low-earth-orbiting satellites (twin AeroCube-6) and near-equatorial satellites (twin Van Allen Probes) are located roughly along the same magnetic field line. By analyzing electron flux variation at various energies (> 35 keV) measured by AeroCube-6 and wave and electron measurements by Van Allen Probes, together with quasilinear diffusion theory and modeling, we determine the physical process of driving the observed energetic electron precipitation for the identified electron precipitation events. Moreover, the twin AeroCube-6 also helps us understand the spatiotemporal effect and constrain the coherent size of each electron precipitation event.

Development of an Atmospheric Pressure Ionization Mass Spectrometer

NASA Technical Reports Server (NTRS)

1998-01-01

A commercial atmospheric pressure ionization mass spectrometer (APIMS) was purchased from EXTREL Mass Spectrometry, Inc. (Pittsburgh, PA). Our research objectives were to adapt this instrument and develop techniques for real-time determinations of the concentrations of trace species in the atmosphere. The prototype instrument is capable of making high frequency measurements with no sample preconcentrations. Isotopically labeled standards are used as an internal standard to obtain high precision and to compensate for changes in instrument sensitivity and analyte losses in the sampling manifold as described by Bandy and coworkers. The prototype instrument is capable of being deployed on NASA C130, Electra, P3, and DC8 aircraft. After purchasing and taking delivery by June 1994, we assembled the mass spectrometer, data acquisition, and manifold flow control instrumentation in electronic racks and performed tests.

A high pressure hollow cathode ionization source for in-situ detection of organic molecules on Mars

NASA Technical Reports Server (NTRS)

Beegle, Luther W.; Kanik, Isik

2001-01-01

We have designed, constructed and characterized a new high-pressure (1-5 Torr) hollow cathode discharge source (HCDSj that can be utilized as an ionizer in a wide variety of mass analyzers. It is able to function under ambient Martian atmospheric conditions without modification.

Correlated electron and nuclear dynamics in strong field photoionization of H(2)(+).

PubMed

Silva, R E F; Catoire, F; Rivière, P; Bachau, H; Martín, F

2013-03-15

We present a theoretical study of H(2)(+) ionization under strong IR femtosecond pulses by using a method designed to extract correlated (2D) photoelectron and proton kinetic energy spectra. The results show two distinct ionization mechanisms-tunnel and multiphoton ionization-in which electrons and nuclei do not share the energy from the field in the same way. Electrons produced in multiphoton ionization share part of their energy with the nuclei, an effect that shows up in the 2D spectra in the form of energy-conservation fringes similar to those observed in weak-field ionization of diatomic molecules. In contrast, tunneling electrons lead to fringes whose position does not depend on the proton kinetic energy. At high intensity, the two processes coexist and the 2D plots show a very rich behavior, suggesting that the correlation between electron and nuclear dynamics in strong field ionization is more complex than one would have anticipated.

Post-flight Analysis of the Argon Filled Ion Chamber

NASA Technical Reports Server (NTRS)

Tai, H.; Goldhagen, P.; Jones, I. W.; Wilson, J. W.; Maiden, D. L.; Shinn, J. L.

2003-01-01

Atmospheric ionizing radiation is a complex mixture of primary galactic and solar cosmic rays and a multitude of secondary particles produced in collision with air nuclei. The first series of Atmospheric Ionizing Radiation (AIR) measurement flights on the NASA research aircraft ER-2 took place in June 1997. The ER-2 flight package consisted of fifteen instruments from six countries and were chosen to provide varying sensitivity to specific components. These AIR ER-2 flight measurements are to characterize the AIR environment during solar minimum to allow the continued development of environmental models of this complex mixture of ionizing radiation. This will enable scientists to study the ionizing radiation health hazard associated with the high-altitude operation of a commercial supersonic transport and to allow estimates of single event upsets for advanced avionics systems design. The argon filled ion chamber representing about 40 percent of the contributions to radiation risks are analyzed herein and model discrepancies for solar minimum environment are on the order of 5 percent and less. Other biologically significant components remain to be analyzed.

Venus - Dead or alive?

NASA Technical Reports Server (NTRS)

Taylor, Harry A., Jr.; Cloutier, Paul A.

1986-01-01

In situ nightside electric field observations from the Pioneer Venus Orbiter have been interpreted as evidence of extensive lightning in the lower atmosphere of Venus. The scenario, including proposed evidence of clustering of lightning over surface highland regions, has encouraged the acceptance of currently active volcanic output as part of several investigations of the dynamics and chemistry of the atmosphere and the geology of the planet. However, the correlation between the 100-hertz electric field events attributed to lightning and nightside ionization troughs resulting from the interaction of the solar wind with the ionosphere indicates that the noise results from locally generated plasma instabilities and not from any behavior of the lower atmosphere. Furthemore, analysis of the spatial distribution of the noise shows that it is not clustered over highland topography, but rather occurs at random throughout the latitude and longitude regions sampled by the orbiter during the first 5 years of operation, from 1978 to 1984. Thus the electric field observations do not identify lightning and do not provide a basis for inferring the presence of currently active volcanic output. In the absence of known evidence to the contrary, it appears that Venus is no longer active.

Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90)

NASA Astrophysics Data System (ADS)

Dierking, Christoph W.; Zurheide, Florian; Zeuch, Thomas; Med, Jakub; Parez, Stanislav; Slavíček, Petr

2017-06-01

Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H2O)n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n <5 . In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (˜2.8 eV) and signal saturation (˜4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n ≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action spectroscopy, based on near threshold photoionization of Na(H2O)n clusters. In addition, simulations of the sodium pick-up process were carried out to study the gradual formation of the hydrated electron which is the basis of the sodium-tagging sizing.

Revealing isomerism in sodium-water clusters: Photoionization spectra of Na(H2O)n (n = 2-90).

PubMed

Dierking, Christoph W; Zurheide, Florian; Zeuch, Thomas; Med, Jakub; Parez, Stanislav; Slavíček, Petr

2017-06-28

Soft ionization of sodium tagged polar clusters is increasingly used as a powerful technique for sizing and characterization of small aerosols with possible application, e.g., in atmospheric chemistry or combustion science. Understanding the structure and photoionization of the sodium doped clusters is critical for such applications. In this work, we report on measurements of photoionization spectra for sodium doped water clusters containing 2-90 water molecules. While most of the previous studies focused on the ionization threshold of the Na(H 2 O) n clusters, we provide for the first time full photoionization spectra, including the high-energy region, which are used as reference for a comparison with theory. As reported in previous work, we have seen an initial drop of the appearance ionization energy with cluster size to values of about 3.2 eV for n<5. In the size range from n = 5 to n = 15, broad ion yield curves emerge; for larger clusters, a constant range between signal appearance (∼2.8 eV) and signal saturation (∼4.1 eV) has been observed. The measurements are interpreted with ab initio calculations and ab initio molecular dynamics simulations for selected cluster sizes (n≤ 15). The simulations revealed theory shortfalls when aiming at quantitative agreement but allowed us identifying structural motifs consistent with the observed ionization energy distributions. We found a decrease in the ionization energy with increasing coordination of the Na atom and increasing delocalization of the Na 3s electron cloud. The appearance ionization energy is determined by isomers with fully solvated sodium and a highly delocalized electron cloud, while both fully and incompletely solvated isomers with localized electron clouds can contribute to the high energy part of the photoionization spectrum. Simulations at elevated temperatures show an increased abundance of isomers with low ionization energies, an entropic effect enabling size selective infrared action spectroscopy, based on near threshold photoionization of Na(H 2 O) n clusters. In addition, simulations of the sodium pick-up process were carried out to study the gradual formation of the hydrated electron which is the basis of the sodium-tagging sizing.

Hydraulic effects in a radiative atmosphere with ionization

NASA Astrophysics Data System (ADS)

Bhat, P.; Brandenburg, A.

2016-03-01

Context. In his 1978 paper, Eugene Parker postulated the need for hydraulic downward motion to explain magnetic flux concentrations at the solar surface. A similar process has also recently been seen in simplified (e.g., isothermal) models of flux concentrations from the negative effective magnetic pressure instability (NEMPI). Aims: We study the effects of partial ionization near the radiative surface on the formation of these magnetic flux concentrations. Methods: We first obtain one-dimensional (1D) equilibrium solutions using either a Kramers-like opacity or the H- opacity. The resulting atmospheres are then used as initial conditions in two-dimensional (2D) models where flows are driven by an imposed gradient force that resembles a localized negative pressure in the form of a blob. To isolate the effects of partial ionization and radiation, we ignore turbulence and convection. Results: Because of partial ionization, an unstable stratification always forms near the surface. We show that the extrema in the specific entropy profiles correspond to the extrema in the degree of ionization. In the 2D models without partial ionization, strong flux concentrations form just above the height where the blob is placed. Interestingly, in models with partial ionization, such flux concentrations always form at the surface well above the blob. This is due to the corresponding negative gradient in specific entropy. Owing to the absence of turbulence, the downflows reach transonic speeds. Conclusions: We demonstrate that, together with density stratification, the imposed source of negative pressure drives the formation of flux concentrations. We find that the inclusion of partial ionization affects the entropy profile dramatically, causing strong flux concentrations to form closer to the surface. We speculate that turbulence effects are needed to limit the strength of flux concentrations and homogenize the specific entropy to a stratification that is close to marginal.

Timing Recollision in Nonsequential Double Ionization by Intense Elliptically Polarized Laser Pulses.

PubMed

Kang, H; Henrichs, K; Kunitski, M; Wang, Y; Hao, X; Fehre, K; Czasch, A; Eckart, S; Schmidt, L Ph H; Schöffler, M; Jahnke, T; Liu, X; Dörner, R

2018-06-01

We examine correlated electron and doubly charged ion momentum spectra from strong field double ionization of neon employing intense elliptically polarized laser pulses. An ellipticity-dependent asymmetry of correlated electron and ion momentum distributions has been observed. Using a 3D semiclassical model, we demonstrate that our observations reflect the subcycle dynamics of the recollision process. Our Letter reveals a general physical picture for recollision impact double ionization with elliptical polarization and demonstrates the possibility of ultrafast control of the recollision dynamics.

Timing Recollision in Nonsequential Double Ionization by Intense Elliptically Polarized Laser Pulses

NASA Astrophysics Data System (ADS)

Kang, H.; Henrichs, K.; Kunitski, M.; Wang, Y.; Hao, X.; Fehre, K.; Czasch, A.; Eckart, S.; Schmidt, L. Ph. H.; Schöffler, M.; Jahnke, T.; Liu, X.; Dörner, R.

2018-06-01

We examine correlated electron and doubly charged ion momentum spectra from strong field double ionization of neon employing intense elliptically polarized laser pulses. An ellipticity-dependent asymmetry of correlated electron and ion momentum distributions has been observed. Using a 3D semiclassical model, we demonstrate that our observations reflect the subcycle dynamics of the recollision process. Our Letter reveals a general physical picture for recollision impact double ionization with elliptical polarization and demonstrates the possibility of ultrafast control of the recollision dynamics.

Enhanced performance for the analysis of prostaglandins and thromboxanes by liquid chromatography-tandem mass spectrometry using a new atmospheric pressure ionization source.

PubMed

Lubin, Arnaud; Geerinckx, Suzy; Bajic, Steve; Cabooter, Deirdre; Augustijns, Patrick; Cuyckens, Filip; Vreeken, Rob J

2016-04-01

Eicosanoids, including prostaglandins and thromboxanes are lipid mediators synthetized from polyunsaturated fatty acids. They play an important role in cell signaling and are often reported as inflammatory markers. LC-MS/MS is the technique of choice for the analysis of these compounds, often in combination with advanced sample preparation techniques. Here we report a head to head comparison between an electrospray ionization source (ESI) and a new atmospheric pressure ionization source (UniSpray). The performance of both interfaces was evaluated in various matrices such as human plasma, pig colon and mouse colon. The UniSpray source shows an increase in method sensitivity up to a factor 5. Equivalent to better linearity and repeatability on various matrices as well as an increase in signal intensity were observed in comparison to ESI. Copyright © 2016 Elsevier B.V. All rights reserved.

Desorption atmospheric pressure photoionization.

PubMed

Haapala, Markus; Pól, Jaroslav; Saarela, Ville; Arvola, Ville; Kotiaho, Tapio; Ketola, Raimo A; Franssila, Sami; Kauppila, Tiina J; Kostiainen, Risto

2007-10-15

An ambient ionization technique for mass spectrometry, desorption atmospheric pressure photoionization (DAPPI), is presented, and its application to the rapid analysis of compounds of various polarities on surfaces is demonstrated. The DAPPI technique relies on a heated nebulizer microchip delivering a heated jet of vaporized solvent, e.g., toluene, and a photoionization lamp emitting 10-eV photons. The solvent jet is directed toward sample spots on a surface, causing the desorption of analytes from the surface. The photons emitted by the lamp ionize the analytes, which are then directed into the mass spectrometer. The limits of detection obtained with DAPPI were in the range of 56-670 fmol. Also, the direct analysis of pharmaceuticals from a tablet surface was successfully demonstrated. A comparison of the performance of DAPPI with that of the popular desorption electrospray ionization method was done with four standard compounds. DAPPI was shown to be equally or more sensitive especially in the case of less polar analytes.

Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.

2011-01-01

Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS n ) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at differentmore » collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.« less

Probing electron delays in above-threshold ionization

DOE PAGES

Zipp, Lucas J.; Natan, Adi; Bucksbaum, Philip H.

2014-11-21

Recent experiments have revealed attosecond delays in the emission of electrons from atoms ionized by extreme UV light, offering a glimpse into the ultrafast nature of light-induced electron dynamics. In this work, we extend these measurements to the strong-field above-threshold ionization (ATI) regime, by measuring delays in the photoemission of electrons from argon in the presence of an intense laser field. We probe the ATI process with a weak coherent reference, at half the laser frequency. The interfering ionization signal reveals the relative spectral phase of adjacent ATI channels, with an equivalent resolution of a few attoseconds. These relative delaysmore » depend on the strong field, and approach zero at higher intensity. Our phase measurements of ATI electrons show how strong fields alter ionization dynamics in atoms.« less

A Collison nebulizer as an ion source for mass spectrometry analysis

NASA Astrophysics Data System (ADS)

Pervukhin, V. V.; Sheven', D. G.; Kolomiets, Yu. N.

2014-12-01

It is proposed to use a Collison nebulizer as a source of ionization for mass-spectrometry with ionization at atmospheric pressure. This source does not require an electric voltage, radioactive sources, heaters, or liquid pumps. It is shown that the number of ions produced by the Collison nebulizer is ten times greater than the quantity of ions produced by the 63Ni radioactive source and three to four times greater than the number of ions produced with sonic ionization devices.

A Numerical Simulation of the Energy Conversion Process in Microwave Rocket

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shibata, Teppei; Oda, Yasuhisa; Komurasaki, Kimiya

2008-04-28

In Microwave Rocket, a high power microwave beam ionizes atmospheric air inside of the thruster and the ionization front drives a shock wave. In this paper, CFD simulation was conducted using measured propagation velocity of the ionization front to evaluate the engine performance. As a result, maximum cycle efficiency was obtained at the power density of about 200 kW/m{sup 2} which is the transitional beam power condition between Microwave Supported Combustion and Microwave Supported Detonation regimes.

Relationship between the Macroscopic and Quantum Characteristics of Dynamic Viscosity for Hydrocarbons upon the Compensation Effect

NASA Astrophysics Data System (ADS)

Dolomatov, M. Yu.; Kovaleva, E. A.; Khamidullina, D. A.

2018-05-01

An approach that allows the calculation of dynamic viscosity for liquid hydrocarbons from quantum (ionization energies) and molecular (Wiener topological indices) parameters is proposed. A physical relationship is revealed between ionization and the energies of viscous flow activation. This relationship is due to the contribution from the dispersion component of Van der Waals forces to intermolecular interaction. A two-parameter dependence of the energy of viscous flow activation, energy of ionization, and Wiener topological indices is obtained. The dynamic viscosities of liquid hydrocarbons can be calculated from the kinetic compensation effect of dynamic viscosity, which indicates a relationship between the energy of activation and the Arrhenius pre-exponental factor of the Frenkel-Eyring hole model. Calculation results are confirmed through statistical processing of the experimental data.

Laser-induced electron dynamics including photoionization: A heuristic model within time-dependent configuration interaction theory.

PubMed

Klinkusch, Stefan; Saalfrank, Peter; Klamroth, Tillmann

2009-09-21

We report simulations of laser-pulse driven many-electron dynamics by means of a simple, heuristic extension of the time-dependent configuration interaction singles (TD-CIS) approach. The extension allows for the treatment of ionizing states as nonstationary states with a finite, energy-dependent lifetime to account for above-threshold ionization losses in laser-driven many-electron dynamics. The extended TD-CIS method is applied to the following specific examples: (i) state-to-state transitions in the LiCN molecule which correspond to intramolecular charge transfer, (ii) creation of electronic wave packets in LiCN including wave packet analysis by pump-probe spectroscopy, and, finally, (iii) the effect of ionization on the dynamic polarizability of H(2) when calculated nonperturbatively by TD-CIS.

Kinetics and Chemistry of Ionization Wave Discharges Propagating Over Dielectric Surfaces

NASA Astrophysics Data System (ADS)

Petrishchev, Vitaly

Experimental studies of near-surface ionization wave electric discharges generated by high peak voltage (20-30 kV), nanosecond duration pulses (full width at half-maximum 50-100 ns) of positive and negative polarity and propagating over dielectric surfaces have been performed. A novel way to sustain diffuse, reproducible, ns pulse surface plasmas at a liquid-vapor interface is demonstrated at buffer gas pressures ranging from 10 to 200 Torr. Generation of surface ionization waves well reproduced shot-to-shot and sustaining diffuse near-surface plasmas is one of the principal advantages of the use of ns pulse discharge waveforms. This makes possible characterization of these plasmas in repetitively pulsed experiments. Numerous applications of these plasmas include low-temperature plasma assisted combustion, plasma fuel reforming, plasma flow control, plasma materials processing, agriculture, biology, and medicine. The objectives of the present work are (i) to demonstrate that surface ionization wave discharge plasmas sustained at a liquid-vapor interface can be used as an experimental platform for studies of near-surface plasma chemical reaction kinetics, at the conditions when the interface acts as a high-yield source of radical species, and (ii) to obtain quantitative insight into dynamics, kinetics and chemistry of surface ionization wave discharges and provide experimental data for validation of kinetic models, to assess their predictive capability. Generation of the initial radical pool may trigger a number of plasma chemical processes leading to formation of a variety of stable product species, depending on the initial composition of the liquid and the buffer gas flow. One of the products formed and detected during surface plasma / liquid water interaction is hydroxyl radical, which is closely relevant to applications of plasmas for biology and medicine. The present work includes detailed studies of surface ionization wave discharges sustained in different buffer gases over solid and liquid dielectric surfaces, such as quartz, distilled water, saline solution, and alcohols, over a wide range of pressures. Specific experiments include: measurements of ionization wave speed; plasma emission imaging using a ns gate camera; detection of surface discharge plasma chemistry products using Fourier transform infrared absorption spectroscopy; surface charge dynamics on short (ns) and long (hundreds of mus) time scales; time-resolved electron density and electron temperature measurements in a ns pulse surface discharge in helium by Thomson scattering; spatially-resolved absolute OH and H atom concentration measurements in ns pulse discharges over distilled water by single-photon and two-photon Laser Induced Fluorescence; and schlieren imaging of perturbations generated by a ns pulse dielectric barrier discharge in a surface plasma actuator in quiescent atmospheric pressure air.

Correlated multielectron dynamics in mid-infrared laser pulse interactions with neon atoms.

PubMed

Tang, Qingbin; Huang, Cheng; Zhou, Yueming; Lu, Peixiang

2013-09-09

The multielectron dynamics in nonsequential triple ionization (NSTI) of neon atoms driven by mid-infrared (MIR) laser pulses is investigated with the three-dimensional classical ensemble model. In consistent with the experimental result, our numerical result shows that in the MIR regime, the triply charged ion longitudinal momentum spectrum exhibits a pronounced double-hump structure at low laser intensity. Back analysis reveals that as the intensity increases, the responsible triple ionization channels transform from direct (e, 3e) channel to the various mixed channels. This transformation of the NSTI channels leads to the results that the shape of ion momentum spectra becomes narrow and the distinct maxima shift towards low momenta with the increase of the laser intensity. By tracing the triply ionized trajectories, the various ionization channels at different laser intensities are clearly identified and these results provide an insight into the complex dynamics of the correlated three electrons in NSTI.

Single electron dynamics in a Hall thruster electromagnetic field profile

NASA Astrophysics Data System (ADS)

Marini, Samuel; Pakter, Renato

2017-05-01

In this work, the single electron dynamics in a simplified three dimensional Hall thruster model is studied. Using Hamiltonian formalism and the concept of limiting curves, one is able to determine confinement conditions for the electron in the acceleration channel. It is shown that as a given parameter of the electromagnetic field is changed, the particle trajectory may transit from regular to chaotic without affecting the confinement, which allows one to make a detailed analysis of the role played by the chaos. The ionization volume is also computed, which measures the probability of an electron to ionize background gas atoms. It is found that there is a great correlation between chaos and increased effective ionization volume. This indicates that a complex dynamical behavior may improve the device efficiency by augmenting the ionization capability of each electron, requiring an overall lower electron current.

Leidenfrost Phenomenon-assisted Thermal Desorption (LPTD) and Its Application to Open Ion Sources at Atmospheric Pressure Mass Spectrometry

NASA Astrophysics Data System (ADS)

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution `Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10-9 M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

Developing of a New Atmospheric Ionizing Radiation (AIR) Model

NASA Technical Reports Server (NTRS)

Clem, John M.; deAngelis, Giovanni; Goldhagen, Paul; Wilson, John W.

2003-01-01

As a result of the research leading to the 1998 AIR workshop and the subsequent analysis, the neutron issues posed by Foelsche et al. and further analyzed by Hajnal have been adequately resolved. We are now engaged in developing a new atmospheric ionizing radiation (AIR) model for use in epidemiological studies and air transportation safety assessment. A team was formed to examine a promising code using the basic FLUKA software but with modifications to allow multiple charged ion breakup effects. A limited dataset of the ER-2 measurements and other cosmic ray data will be used to evaluate the use of this code.

Ionization source utilizing a jet disturber in combination with an ion funnel and method of operation

DOEpatents

Smith, Richard D.; Kim, Taeman; Tang, Keqi; Udseth, Harold R.

2003-06-24

A jet disturber used in combination with an ion funnel to focus ions and other charged particles generated at or near atmospheric pressure into a relatively low pressure region, which allows increased conductance of the ions and other charged particles. The jet disturber is positioned within an ion funnel and may be interfaced with a multi-capillary inlet juxtaposed between an ion source and the interior of an instrument maintained at near atmospheric pressure. The invention finds particular advantages when deployed to improve the ion transmission between an electrospray ionization source and the first vacuum stage of a mass spectrometer.

A comparison of flame ionization and ozone chemiluminescence for the determination of atmospheric hydrocarbons.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marley, N. A.; Gaffney, J. S.; Environmental Research

A reactive hydrocarbon analyzer has been constructed on the basis of chemiluminescence reaction with ozone. This detector is designed to operate at varying temperatures which take advantage of the different rates of reaction of the hydrocarbon classes with ozone to yield a measure of their atmospheric reactivity. When operated at high temperatures (170 C), all hydrocarbons will give a chemiluminescence signal. Reported here is a direct comparison of the ozone chemiluminescent detector (operated at a temperature of 170 C) with a flame ionization detector. This comparison was accomplished by connecting a capillary gas chromatograph to each of the two detectorsmore » by means of a switching valve. Twenty-seven compounds representing alkanes, alkenes, aromatics, and oxygenated hydrocarbons (aldehydes, ketones, alcohols, and ethers) were studied. For the compounds studied, analytical sensitivities were 10-1000 times better for the chemiluminescence detector. The results of this comparison indicate that the response of the chemiluminescent detector at 170 C correlates with a total carbon detector (flame ionization detection) and that total response is a measure of total carbon in the sample. The chemiluminescent system will be very useful for gas chromatographic detection of atmospheric hydrocarbons, particularly of oxygenates in complex mixtures.« less

Determination of polycyclic aromatic hydrocarbons in fractions in asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

2015-07-01

An analytical method using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization for the determination of polycyclic aromatic hydrocarbons in asphalt fractions has been developed. The 14 compounds determined, characterized by having two or more condensed aromatic rings, are expected to be present in asphalt and are considered carcinogenic and mutagenic. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all of the compounds. The limits of detection ranged from 0.5 to 346.5 μg/L and the limits of quantification ranged from 1.7 to 1550 μg/L. The method was validated against a diesel particulate extract standard reference material (NIST SRM 1975), and the obtained concentrations agreed with the certified values. The method was applied to asphalt samples after its fractionation according to ASTM D4124 and the method of Green. The concentrations of the seven polycyclic aromatic hydrocarbons quantified in the sample ranged from 0.86 mg/kg for benzo[ghi]perylene to 98.32 mg/kg for fluorene. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Estimation of NOx Production from Terrestrial Gamma-ray Flashes

NASA Astrophysics Data System (ADS)

Cramer, E. S.; Briggs, M. S.; Liu, N.; Mailyan, B.; Rassoul, H.; Dwyer, J. R.

2016-12-01

The motivation of this work is to understand the effects of TGFs on the ozone layer. One of the main ozone-destroying mechanisms is the production of NOx in the stratospheric region. We first review the mechanisms for NOx production in this region, specifically looking at the global rate produced by lightning. Terrestrial Gamma-ray Flashes, with runaway electron avalanches and the subsequent bremsstrahlung gamma rays, produce atmospheric ionization at all altitudes of the atmosphere. TGFs might have a greater impact on the ozone concentration in the stratosphere since they directly produce ionization and thus NOx in the ozone layer. In order to study the effect from TGFs, we use the runaway electron avalanche model (REAM) to simulate a typical TGF. The photons are then transported through Earth's atmosphere, where they deposit some of their energy as ionization in the ozone layer. We then calculate the number of NOx molecules produced by considering the average energy required to produce one electron-ion pair (W = 35 eV). The W factor has been experimentally quantified and is constant for various types of radiation and over large energy ranges and electric fields. Finally, the effect of TGF NOx production is estimated using the global annual rate of TGFs.

Atmospheric NLTE models for the spectroscopic analysis of blue stars with winds. III. X-ray emission from wind-embedded shocks

NASA Astrophysics Data System (ADS)

Carneiro, L. P.; Puls, J.; Sundqvist, J. O.; Hoffmann, T. L.

2016-05-01

Context. Extreme ultraviolet (EUV) and X-ray radiation emitted from wind-embedded shocks in hot, massive stars can affect the ionization balance in their outer atmospheres and can be the mechanism responsible for producing highly ionized atomic species detected in stellar wind UV spectra. Aims: To allow for these processes in the context of spectral analysis, we have implemented the emission from wind-embedded shocks and related physics into our unified, NLTE model atmosphere/spectrum synthesis code FASTWIND. Methods: The shock structure and corresponding emission is calculated as a function of user-supplied parameters (volume filling factor, radial stratification of shock strength, and radial onset of emission). We account for a temperature and density stratification inside the postshock cooling zones, calculated for radiative and adiabatic cooling in the inner and outer wind, respectively. The high-energy absorption of the cool wind is considered by adding important K-shell opacities, and corresponding Auger ionization rates have been included in the NLTE network. To test our implementation and to check the resulting effects, we calculated a comprehensive model grid with a variety of X-ray emission parameters. Results: We tested and verified our implementation carefully against corresponding results from various alternative model atmosphere codes, and studied the effects from shock emission for important ions from He, C, N, O, Si, and P. Surprisingly, dielectronic recombination turned out to play an essential role for the ionization balance of O iv/O v (particularly in dwarfs with Teff~ 45 000 K). Finally, we investigated the frequency dependence and radial behavior of the mass absorption coefficient, κν(r), which is important in the context of X-ray line formation in massive star winds. Conclusions: In almost all of the cases considered, direct ionization is of major influence because of the enhanced EUV radiation field, and Auger ionization only affects N vi and O vi significantly. The approximation of a radially constant κν is justified for r ≳ 1.2 R∗ and λ ≲ 18 Å and also for many models at longer wavelengths. To estimate the actual value of this quantity, however, the He II opacities need to be calculated from detailed NLTE modeling, at least for wavelengths longer than 18 to 20 Å, and information on the individual CNO abundances has to be present.

Modeling of metal thin film growth: Linking angstrom-scale molecular dynamics results to micron-scale film topographies

NASA Astrophysics Data System (ADS)

Hansen, U.; Rodgers, S.; Jensen, K. F.

2000-07-01

A general method for modeling ionized physical vapor deposition is presented. As an example, the method is applied to growth of an aluminum film in the presence of an ionized argon flux. Molecular dynamics techniques are used to examine the surface adsorption, reflection, and sputter reactions taking place during ionized physical vapor deposition. We predict their relative probabilities and discuss their dependence on energy and incident angle. Subsequently, we combine the information obtained from molecular dynamics with a line of sight transport model in a two-dimensional feature, incorporating all effects of reemission and resputtering. This provides a complete growth rate model that allows inclusion of energy- and angular-dependent reaction rates. Finally, a level-set approach is used to describe the morphology of the growing film. We thus arrive at a computationally highly efficient and accurate scheme to model the growth of thin films. We demonstrate the capabilities of the model predicting the major differences on Al film topographies between conventional and ionized sputter deposition techniques studying thin film growth under ionized physical vapor deposition conditions with different Ar fluxes.

Do stellar and nebular abundances in the Cocoon nebula agree?

NASA Astrophysics Data System (ADS)

García-Rojas, J.; Simón-Díaz, S.; Esteban, C.

2015-05-01

The Cocoon nebula is an apparently spherical Galactic HII region ionized by a single star (BD+46 3474). This nebula seems to be appropriate to investigate the chemical behavior of oxygen and other heavy elements from two different points of view: a detailed analysis of the chemical content of the ionized gas through nebular spectrophotometry and a detailed spectroscopic analysis of the spectrum of the ionizing star using the state-of-the-art stellar atmosphere modelling. In this poster we present the results from a set of high-quality observations, from 2m-4m class telescopes, including the optical spectrum of the ionizing star BD+46 3474, along with long-slit spatially resolved spectroscopy of the nebula. We have used state-of-the-art stellar atmosphere codes to determine stellar parameters and the chemical content of several heavy elements. Traditional nebular techniques along with updated atomic data have been used to compute gaseous abundances of O, N and S in the Cocoon nebula. Thanks to the low ionization degree of the nebula, we could determine total abundances directly from observable ions (no ionization correction factors were needed) for three of the analyzed elements (O, S, and N). The derived stellar and nebular abundances are compared and the influence of the possible presence of the so-called temperature fluctuations on the nebula is discussed. The results of this study are presented in more detail in García-Rojas, Simón-Díaz & Esteban 2014, A&A, 571, A93.

Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS)

PubMed Central

Benigni, Paolo; DeBord, J. Daniel; Thompson, Christopher J.; Gardinali, Piero; Fernandez-Lima, Francisco

2016-01-01

Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the m/z 100–450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation. PMID:27212790

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hu, S. X., E-mail: shu@lle.rochester.edu; Goncharov, V. N.; McCrory, R. L.

2016-04-15

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations of the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm{sup 3} and T = 15 625 to 500 000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which gives an increasing ionization as the CH density increases even at low temperatures (T < 50 eV). The orbital-free molecular dynamics method is only used to gauge the average ionization behavior of CH under the average-atommore » model in conjunction with the pressure-matching mixing rule. The thermal conductivities (κ{sub QMD}) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted with a generalized Coulomb logarithm [(lnΛ){sub QMD}] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted ∼20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Characteristics of plasma plume in ultrafast laser ablation with a weakly ionized air channel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hou, Huaming; Yang, Bo; Mao, Xianglei

We report the influence of femtosecond (fs) laser weakly ionized air channel on characteristics of plasma induced from fs-laser ablation of solid Zr metal target. A novel method to create high temperature, low electron density plasma with intense elemental emission and weak bremsstrahlung emission was demonstrated. Weakly ionized air channel was generated as a result of a non-linear phenomenon. Two-dimensional time-resolved optical-emission images of plasma plumes were taken for plume dynamics analysis. Dynamic physical properties of filament channels were simulated. In particular, we investigated the influence of weakly ionized air channel on the evolution of solid plasma plume. Plasma plumemore » splitting was observed whilst longer weakly ionized air channel formed above the ablation spot. The domination mechanism for splitting is attributed to the long-lived underdense channel created by fs-laser induced weakly ionization of air. The evolutions of atomic/molecular emission intensity, peak broadening, and plasma temperature were analyzed, and the results show that the part of plasma entering weakly ionized air channel features higher initial temperature, lower electron density and faster decay.« less

Characteristics of plasma plume in ultrafast laser ablation with a weakly ionized air channel

DOE PAGES

Hou, Huaming; Yang, Bo; Mao, Xianglei; ...

2018-05-10

We report the influence of femtosecond (fs) laser weakly ionized air channel on characteristics of plasma induced from fs-laser ablation of solid Zr metal target. A novel method to create high temperature, low electron density plasma with intense elemental emission and weak bremsstrahlung emission was demonstrated. Weakly ionized air channel was generated as a result of a non-linear phenomenon. Two-dimensional time-resolved optical-emission images of plasma plumes were taken for plume dynamics analysis. Dynamic physical properties of filament channels were simulated. In particular, we investigated the influence of weakly ionized air channel on the evolution of solid plasma plume. Plasma plumemore » splitting was observed whilst longer weakly ionized air channel formed above the ablation spot. The domination mechanism for splitting is attributed to the long-lived underdense channel created by fs-laser induced weakly ionization of air. The evolutions of atomic/molecular emission intensity, peak broadening, and plasma temperature were analyzed, and the results show that the part of plasma entering weakly ionized air channel features higher initial temperature, lower electron density and faster decay.« less

Ionization of Rydberg atoms colliding with a metal surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sjakste, J.; Borisov, A. G.; Gauyacq, J. P.

2006-04-15

We report on a theoretical study of the ionization process of Xe* Rydberg atoms colliding with a metal surface, in the presence of an external electric field. The evolution of the Xe* outer electron is studied by a wave packet propagation approach, allowing to include all dynamical aspects of the collision, in particular nonadiabatic inter-Rydberg transitions. We investigate how the different Xe* Stark states formed in the external field couple together and ionize on the surface and how the different polarizations of the electronic cloud in the Xe* states are reflected in their ionization properties. We show that the presencemore » of the external electric field can significantly perturb the dynamics of the ionization process. Our results account for recent results from Dunning et al. [Nucl. Inst. Meth. B 203, 69 (2003)]. In particular, it is explained how the external electric field present in the experimental procedure of Dunning et al. leads to the apparent absence of a polarization effect in the ionization process.« less

Separation and identification of corticosterone metabolites by liquid chromatography--electrospray ionization mass spectrometry.

PubMed

Miksík, I; Vylitová, M; Pácha, J; Deyl, Z

1999-04-16

High-performance liquid chromatography coupled to atmospheric pressure ionization-electrospray ionization mass spectrometry (API-ESI-MS) was investigated for the analysis of corticosterone metabolites; their characterization was obtained by combining the separation on Zorbax Eclipse XDB C18 column (eluted with a methanol-water-acetic acid gradient) with identification using positive ion mode API-ESI-MS and selected ion analysis. The applicability of this method was verified by monitoring the activity of steroid converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in avian intestines.

Impact ionization study

NASA Technical Reports Server (NTRS)

Whipple, E. C., Jr.

1982-01-01

The impact ionization phenomenon which was observed on certain spacecraft was studied. The phenomenon occurs when a neutral atom, molecule, or ion strikes a surface with sufficient kinetic energy that either the incident neutral or atoms on the surface are ionized, with subsequent escape of ions and/or electrons. The released ions and electrons can interfere with measurements on the spacecraft by confusing interpretation of the data. On the other hand, there is the possibility that the effect could be developed into a diagnostic tool for investigating neutral atmospheric species or for studying physical processes on spacecraft surfaces.

Strategic Directions in Heliophysics Research Related to Weakly Ionized Plasmas

NASA Technical Reports Server (NTRS)

Spann, James F.

2010-01-01

In 2009, the Heliophysics Division of NASA published its triennial roadmap entitled "Heliophysics; the solar and space physics of a new era." In this document contains a science priority that is recommended that will serve as input into the recently initiated NRC Heliophysics Decadal Survey. The 2009 roadmap includes several science targets recommendations that are directly related to weakly ionized plasmas, including on entitled "Ion-Neutral Coupling in the Atmosphere." This talk will be a brief overview of the roadmap with particular focus on the science targets relevant to weakly ionized plasmas.

Level 2 processing for the imaging Fourier transform spectrometer GLORIA: derivation and validation of temperature and trace gas volume mixing ratios from calibrated dynamics mode spectra

NASA Astrophysics Data System (ADS)

Ungermann, J.; Blank, J.; Dick, M.; Ebersoldt, A.; Friedl-Vallon, F.; Giez, A.; Guggenmoser, T.; Höpfner, M.; Jurkat, T.; Kaufmann, M.; Kaufmann, S.; Kleinert, A.; Krämer, M.; Latzko, T.; Oelhaf, H.; Olchewski, F.; Preusse, P.; Rolf, C.; Schillings, J.; Suminska-Ebersoldt, O.; Tan, V.; Thomas, N.; Voigt, C.; Zahn, A.; Zöger, M.; Riese, M.

2015-06-01

The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) is an airborne infrared limb imager combining a two-dimensional infrared detector with a Fourier transform spectrometer. It was operated aboard the new German Gulfstream G550 High Altitude LOng Range (HALO) research aircraft during the Transport And Composition in the upper Troposphere/lowermost Stratosphere (TACTS) and Earth System Model Validation (ESMVAL) campaigns in summer 2012. This paper describes the retrieval of temperature and trace gas (H2O, O3, HNO3) volume mixing ratios from GLORIA dynamics mode spectra that are spectrally sampled every 0.625 cm-1. A total of 26 integrated spectral windows are employed in a joint fit to retrieve seven targets using consecutively a fast and an accurate tabulated radiative transfer model. Typical diagnostic quantities are provided including effects of uncertainties in the calibration and horizontal resolution along the line of sight. Simultaneous in situ observations by the Basic Halo Measurement and Sensor System (BAHAMAS), the Fast In-situ Stratospheric Hygrometer (FISH), an ozone detector named Fairo, and the Atmospheric chemical Ionization Mass Spectrometer (AIMS) allow a validation of retrieved values for three flights in the upper troposphere/lowermost stratosphere region spanning polar and sub-tropical latitudes. A high correlation is achieved between the remote sensing and the in situ trace gas data, and discrepancies can to a large extent be attributed to differences in the probed air masses caused by different sampling characteristics of the instruments. This 1-D processing of GLORIA dynamics mode spectra provides the basis for future tomographic inversions from circular and linear flight paths to better understand selected dynamical processes of the upper troposphere and lowermost stratosphere.

Level 2 processing for the imaging Fourier transform spectrometer GLORIA: derivation and validation of temperature and trace gas volume mixing ratios from calibrated dynamics mode spectra

NASA Astrophysics Data System (ADS)

Ungermann, J.; Blank, J.; Dick, M.; Ebersoldt, A.; Friedl-Vallon, F.; Giez, A.; Guggenmoser, T.; Höpfner, M.; Jurkat, T.; Kaufmann, M.; Kaufmann, S.; Kleinert, A.; Krämer, M.; Latzko, T.; Oelhaf, H.; Olchewski, F.; Preusse, P.; Rolf, C.; Schillings, J.; Suminska-Ebersoldt, O.; Tan, V.; Thomas, N.; Voigt, C.; Zahn, A.; Zöger, M.; Riese, M.

2014-12-01

The Gimballed Limb Observer for Radiance Imaging of the Atmosphere (GLORIA) is an airborne infrared limb-imager combining a two-dimensional infrared detector with a Fourier transform spectrometer. It was operated aboard the new German Gulfstream G550 research aircraft HALO during the Transport And Composition in the upper Troposphere/lowermost Stratosphere (TACTS) and Earth System Model Validation (ESMVAL) campaigns in summer 2012. This paper describes the retrieval of temperature and trace gas (H2O, O3, HNO3) volume mixing ratios from GLORIA dynamics mode spectra. 26 integrated spectral windows are employed in a joint fit to retrieve seven targets using consecutively a fast and an accurate tabulated radiative transfer model. Typical diagnostic quantities are provided including effects of uncertainties in the calibration and horizontal resolution along the line-of-sight. Simultaneous in-situ observations by the BAsic HALO Measurement And Sensor System (BAHAMAS), the Fast In-Situ Stratospheric Hygrometer (FISH), FAIRO, and the Atmospheric chemical Ionization Mass Spectrometer (AIMS) allow a validation of retrieved values for three flights in the upper troposphere/lowermost stratosphere region spanning polar and sub-tropical latitudes. A high correlation is achieved between the remote sensing and the in-situ trace gas data, and discrepancies can to a large fraction be attributed to differences in the probed air masses caused by different sampling characteristics of the instruments. This 1-D processing of GLORIA dynamics mode spectra provides the basis for future tomographic inversions from circular and linear flight paths to better understand selected dynamical processes of the upper troposphere and lowermost stratosphere.

Influence of ionization on ultrafast gas-based nonlinear fiber optics.

PubMed

Chang, W; Nazarkin, A; Travers, J C; Nold, J; Hölzer, P; Joly, N Y; Russell, P St J

2011-10-10

We numerically investigate the effect of ionization on ultrashort high-energy pulses propagating in gas-filled kagomé-lattice hollow-core photonic crystal fibers by solving an established uni-directional field equation. We consider the dynamics of two distinct regimes: ionization induced blue-shift and resonant dispersive wave emission in the deep-UV. We illustrate how the system evolves between these regimes and the changing influence of ionization. Finally, we consider the effect of higher ionization stages.

Direct olive oil analysis by mass spectrometry: A comparison of different ambient ionization methods.

PubMed

Lara-Ortega, Felipe J; Beneito-Cambra, Miriam; Robles-Molina, José; García-Reyes, Juan F; Gilbert-López, Bienvenida; Molina-Díaz, Antonio

2018-04-01

Analytical methods based on ambient ionization mass spectrometry (AIMS) combine the classic outstanding performance of mass spectrometry in terms of sensitivity and selectivity along with convenient features related to the lack of sample workup required. In this work, the performance of different mass spectrometry-based methods has been assessed for the direct analyses of virgin olive oil for quality purposes. Two sets of experiments have been setup: (1) direct analysis of untreated olive oil using AIMS methods such as Low-Temperature Plasma Mass Spectrometry (LTP-MS) or paper spray mass spectrometry (PS-MS); or alternatively (2) the use of atmospheric pressure ionization (API) mass spectrometry by direct infusion of a diluted sample through either atmospheric pressure chemical ionization (APCI) or electrospray (ESI) ionization sources. The second strategy involved a minimum sample work-up consisting of a simple olive oil dilution (from 1:10 to 1:1000) with appropriate solvents, which originated critical carry over effects in ESI, making unreliable its use in routine; thus, ESI required the use of a liquid-liquid extraction to shift the measurement towards a specific part of the composition of the edible oil (i.e. polyphenol rich fraction or lipid/fatty acid profile). On the other hand, LTP-MS enabled direct undiluted mass analysis of olive oil. The use of PS-MS provided additional advantages such as an extended ionization coverage/molecular weight range (compared to LTP-MS) and the possibility to increase the ionization efficiency towards nonpolar compounds such as squalene through the formation of Ag + adducts with carbon-carbon double bounds, an attractive feature to discriminate between oils with different degree of unsaturation. Copyright © 2017 Elsevier B.V. All rights reserved.

Systematic investigation of ion suppression and enhancement effects of fourteen stable-isotope-labeled internal standards by their native analogues using atmospheric-pressure chemical ionization and electrospray ionization and the relevance for multi-analyte liquid chromatographic/mass spectrometric procedures.

PubMed

Remane, Daniela; Wissenbach, Dirk K; Meyer, Markus R; Maurer, Hans H

2010-04-15

In clinical and forensic toxicology, multi-analyte procedures are very useful to quantify drugs and poisons of different classes in one run. For liquid chromatographic/tandem mass spectrometric (LC/MS/MS) multi-analyte procedures, often only a limited number of stable-isotope-labeled internal standards (SIL-ISs) are available. If an SIL-IS is used for quantification of other analytes, it must be excluded that the co-eluting native analyte influences its ionization. Therefore, the effect of ion suppression and enhancement of fourteen SIL-ISs caused by their native analogues has been studied. It could be shown that the native analyte concentration influenced the extent of ion suppression and enhancement effects leading to more suppression with increasing analyte concentration especially when electrospray ionization (ESI) was used. Using atmospheric-pressure chemical ionization (APCI), methanolic solution showed mainly enhancement effects, whereas no ion suppression and enhancement effect, with one exception, occurred when plasma extracts were used under these conditions. Such differences were not observed using ESI. With ESI, eleven SIL-ISs showed relevant suppression effects, but only one analyte showed suppression effects when APCI was used. The presented study showed that ion suppression and enhancement tests using matrix-based samples of different sources are essential for the selection of ISs, particularly if used for several analytes to avoid incorrect quantification. In conclusion, only SIL-ISs should be selected for which no suppression and enhancement effects can be observed. If not enough ISs are free of ionization interferences, a different ionization technique should be considered. 2010 John Wiley & Sons, Ltd.

Mass spectrometric behavior of anabolic androgenic steroids using gas chromatography coupled to atmospheric pressure chemical ionization source. Part I: ionization.

PubMed

Raro, M; Portolés, T; Sancho, J V; Pitarch, E; Hernández, F; Marcos, J; Ventura, R; Gómez, C; Segura, J; Pozo, O J

2014-06-01

The detection of anabolic androgenic steroids (AAS) is one of the most important topics in doping control analysis. Gas chromatography coupled to (tandem) mass spectrometry (GC-MS(/MS)) with electron ionization and liquid chromatography coupled to tandem mass spectrometry have been traditionally applied for this purpose. However, both approaches still have important limitations, and, therefore, detection of all AAS is currently afforded by the combination of these strategies. Alternative ionization techniques can minimize these drawbacks and help in the implementation of a single method for the detection of AAS. In the present work, a new atmospheric pressure chemical ionization (APCI) source commercialized for gas chromatography coupled to a quadrupole time-of-flight analyzer has been tested to evaluate the ionization of 60 model AAS. Underivatized and trimethylsylil (TMS)-derivatized compounds have been investigated. The use of GC-APCI-MS allowed for the ionization of all AAS assayed irrespective of their structure. The presence of water in the source as modifier promoted the formation of protonated molecules ([M+H](+)), becoming the base peak of the spectrum for the majority of studied compounds. Under these conditions, [M+H](+), [M+H-H2O](+) and [M+H-2·H2O](+) for underivatized AAS and [M+H](+), [M+H-TMSOH](+) and [M+H-2·TMSOH](+) for TMS-derivatized AAS were observed as main ions in the spectra. The formed ions preserve the intact steroid skeleton, and, therefore, they might be used as specific precursors in MS/MS-based methods. Additionally, a relationship between the relative abundance of these ions and the AAS structure has been established. This relationship might be useful in the structural elucidation of unknown metabolites. Copyright © 2014 John Wiley & Sons, Ltd.

Microplasma-based flowing atmospheric-pressure afterglow (FAPA) source for ambient desorption-ionization mass spectrometry.

PubMed

Zeiri, Offer M; Storey, Andrew P; Ray, Steven J; Hieftje, Gary M

2017-02-01

A new direct-current microplasma-based flowing atmospheric pressure afterglow (FAPA) source was developed for use in ambient desorption-ionization mass spectrometry. The annular-shaped microplasma is formed in helium between two concentric stainless-steel capillaries that are separated by an alumina tube. Current-voltage characterization of the source shows that this version of the FAPA operates in the normal glow-discharge regime. A glass surface placed in the path of the helium afterglow reaches temperatures of up to approximately 400 °C; the temperature varies with distance from the source and helium flow rate through the source. Solid, liquid, and vapor samples were examined by means of a time-of-flight mass spectrometer. Results suggest that ionization occurs mainly through protonation, with only a small amount of fragmentation and adduct formation. The mass range of the source was shown to extend up to at least m/z 2722 for singly charged species. Limits of detection for several small organic molecules were in the sub-picomole range. Examination of competitive ionization revealed that signal suppression occurs only at high (mM) concentrations of competing substances. Copyright © 2016 Elsevier B.V. All rights reserved.

Detection of positive and negative ions from a flowing atmospheric pressure afterglow using a Mattauch-Herzog mass spectrograph equipped with a Faraday-strip array detector.

PubMed

Schilling, Gregory D; Shelley, Jacob T; Barnes, James H; Sperline, Roger P; Denton, M Bonner; Barinaga, Charles J; Koppenaal, David W; Hieftje, Gary M

2010-01-01

An ambient desorption/ionization (ADI) source, known as the flowing atmospheric pressure afterglow (FAPA), has been coupled to a Mattauch-Herzog mass spectrograph (MHMS) equipped with a focal plane camera (FPC) array detector. The FAPA ionization source enables direct mass spectral analysis of solids, liquids, and gases through either positive or negative ionization modes. In either case, spectra are generally simple with dominant peaks being the molecular ions or protonated molecular ions. Use of the FAPA source with the MHMS allows the FPC detector to be characterized for the determination of molecular species, whereas previously only atomic mass spectrometry (MS) has been demonstrated. Furthermore, the FPC is shown to be sensitive to negative ions without the need to change any detector parameters. The analysis of solid, liquid, and gaseous samples through positive and negative ionization is demonstrated with detection limits (1-25 fmol/s, approximately 0.3-10 pg of analyte per mL of helium) surpassing those obtained with the FAPA source coupled to a time-of-flight mass analyzer. 2010 American Society for Mass Spectrometry. Published by Elsevier Inc. All rights reserved.

SFC-APLI-(TOF)MS: Hyphenation of Supercritical Fluid Chromatography to Atmospheric Pressure Laser Ionization Mass Spectrometry.

PubMed

Klink, Dennis; Schmitz, Oliver Johannes

2016-01-05

Atmospheric-pressure laser ionization mass spectrometry (APLI-MS) is a powerful method for the analysis of polycyclic aromatic hydrocarbon (PAH) molecules, which are ionized in a selective and highly sensitive way via resonance-enhanced multiphoton ionization. APLI was presented in 2005 and has been hyphenated successfully to chromatographic separation techniques like high performance liquid chromatography (HPLC) and gas chromatography (GC). In order to expand the portfolio of chromatographic couplings to APLI, a new hyphenation setup of APLI and supercritical-fluid chromatography (SFC) was constructed and aim of this work. Here, we demonstrate the first hyphenation of SFC and APLI in a simple designed way with respect to different optimization steps to ensure a sensitive analysis. The new setup permits qualitative and quantitative determination of native and also more polar PAH molecules. As a result of the altered ambient characteristics within the source enclosure, the quantification of 1-hydroxypyrene (1-HP) in human urine is possible without prior derivatization. The limit of detection for 1-HP by SFC-APLI-TOF(MS) was found to be 0.5 μg L(-1), which is lower than the 1-HP concentrations found in exposed persons.

Shock Wave Dynamics in Weakly Ionized Plasmas

NASA Technical Reports Server (NTRS)

Johnson, Joseph A., III

1999-01-01

An investigation of the dynamics of shock waves in weakly ionized argon plasmas has been performed using a pressure ruptured shock tube. The velocity of the shock is observed to increase when the shock traverses the plasma. The observed increases cannot be accounted for by thermal effects alone. Possible mechanisms that could explain the anomalous behavior include a vibrational/translational relaxation in the nonequilibrium plasma, electron diffusion across the shock front resulting from high electron mobility, and the propagation of ion-acoustic waves generated at the shock front. Using a turbulence model based on reduced kinetic theory, analysis of the observed results suggest a role for turbulence in anomalous shock dynamics in weakly ionized media and plasma-induced hypersonic drag reduction.

Radiative properties of molecular nitrogen ions produced by helium Penning ionization and argon effects

NASA Technical Reports Server (NTRS)

Miller, George, III; Song, Kyo-Dong

1994-01-01

The development of hypersonic aerospace vehicles requires a better understanding on the thermal and chemical nonequilibrium kinetics of participating species in shock layers. The computational fluid dynamic (CFD) codes developed for such flowfields overestimate the radiation in the spectral region of 300 - 600 nm. A speculation for this overestimation is that inclusion of Ar, CO2, and H2O at the upper atmosphere flight region makes a significant impact on radiative kinetics of molecular nitrogen ions. To define the effects of minority species on the radiative kinetics of N2(+), an experimental setup was made by using the helium Penning ionization. The vibrational and rotational temperature were measured by mapping the vibrational and rotational distributions of N2(+) emission with high spectroscopic resolution and absolute intensity measurements. Measured vibrational temperatures were in the range from 18,000 to 36,000 K, and rotational temperatures were in the range from 300 to 370 K. The irradiance of 391.44 nm line and rotational and vibrational temperatures were analyzed to define argon and CO2 effects on the N2(+) emission. When Ar or CO2 is injected with N2, the rotational temperature did not change. The irradiances were reduced by 34 percent and 78 percent for the 50 percent of mixture of Ar and CO2, respectively. The vibrational temperatures were increased by 24.1 percent and 82.9 percent for the 50 percent of mixture of Ar and CO2, respectively. It appears that there are no significant effects from small concentrations of Ar and CO2 at the upper atmosphere flight region.

Prototype Operational Advances for Atmospheric Radiation Dose Rate Specification

NASA Astrophysics Data System (ADS)

Tobiska, W. K.; Bouwer, D.; Bailey, J. J.; Didkovsky, L. V.; Judge, K.; Garrett, H. B.; Atwell, W.; Gersey, B.; Wilkins, R.; Rice, D.; Schunk, R. W.; Bell, D.; Mertens, C. J.; Xu, X.; Crowley, G.; Reynolds, A.; Azeem, I.; Wiltberger, M. J.; Wiley, S.; Bacon, S.; Teets, E.; Sim, A.; Dominik, L.

2014-12-01

Space weather's effects upon the near-Earth environment are due to dynamic changes in the energy transfer processes from the Sun's photons, particles, and fields. The coupling between the solar and galactic high-energy particles, the magnetosphere, and atmospheric regions can significantly affect humans and our technology as a result of radiation exposure. Space Environment Technologies (SET) has developed innovative, new space weather observations that will become part of the toolset that is transitioned into operational use. One prototype operational system for providing timely information about the effects of space weather is SET's Automated Radiation Measurements for Aerospace Safety (ARMAS) system. ARMAS will provide the "weather" of the radiation environment to improve aircraft crew and passenger safety. Through several dozen flights the ARMAS project has successfully demonstrated the operation of a micro dosimeter on commercial aviation altitude aircraft that captures the real-time radiation environment resulting from Galactic Cosmic Rays and Solar Energetic Particles. The real-time radiation exposure is computed as an effective dose rate (body-averaged over the radiative-sensitive organs and tissues in units of microsieverts per hour); total ionizing dose is captured on the aircraft, downlinked in real-time via Iridium satellites, processed on the ground into effective dose rates, compared with NASA's Langley Research Center (LaRC) most recent Nowcast of Atmospheric Ionizing Radiation System (NAIRAS) global radiation climatology model runs, and then made available to end users via the web and smart phone apps. We are extending the dose measurement domain above commercial aviation altitudes into the stratosphere with a collaborative project organized by NASA's Armstrong Flight Research Center (AFRC) called Upper-atmospheric Space and Earth Weather eXperiment (USEWX). In USEWX we will be flying on the ER-2 high altitude aircraft a micro dosimeter for effective dose rate measurements and a thermal neutron monitor to characterize Single Event Effects (SEEs) in avionics. In this presentation we describe recent ARMAS and USEWX advances that will ultimately provide operational users with real-time dose and dose rate data for human tissue and avionics exposure risk mitigation.

Flight mechanics applications for tethers in space: Cooperative Italian-US programs

NASA Technical Reports Server (NTRS)

Bevilacqua, Franco; Merlina, Pietro; Anderson, John L.

1990-01-01

Since the 1974 proposal by Giuseppe Colombo to fly a tethered subsatellite from the Shuttle Orbiter, the creative thinking of many scientists and engineers from Italy and U.S. has generated a broad range of potential tether applications in space. Many of these applications have promise for enabling innovative research and operational activities relating to flight mechanics in earth orbit and at suborbital altitudes. From a flight mechanics standpoint the most interesting of the currently proposed flight demonstrations are: the second Tethered Satellite System experiment which offers both the potential for aerothermodynamics and hypersonics research and for atmospheric science research; the Tethered Initiated Space Recovery System which would enable orbital deboost and recovery of a re-entry vehicle and waste removal from a space station; and the Tether Elevator/Crawler System which would provide a variable microgravity environment and space station center of mass management. The outer atmospheric and orbital flight mechanics characteristics of these proposed tether flight demonstrations are described. The second Tethered Satellite System mission will deploy the tethered satellite earthward and will bring it as low as 130 km from ground and thus into the transition region between the atmosphere (non-ionized) and the partially ionized ionosphere. The atmospheric flight mechanics of the tethered satellite is discussed and simulation results are presented. The Tether Initiated Space Recovery System experiment will demonstrate the ability of a simple tether system to deboost and recover a reentry vehicle. The main feature of this demonstration is the utilization of a Small Expendable Deployment System (SEDS) and the low-tension deployment assumed to separate the reentry vehicle from the Shuttle. This low-tension deployment maneuver is discussed and its criticalities are outlined. The Tether Elevator/Crawler System is a new space element able to move in a controlled way between the ends of a deployed tethered system. A Shuttle test of an Elevator model is planned to demonstrate the unique capability of this element as a microgravity facility and to test the transfer motion control. The basic dynamical features of the Elevator system are presented and a preliminary assessment of the Elevator-induced tether vibrations is discussed.

Determination of glucosinolates in rapeseed and Thlaspi caerulescens plants by liquid chromatography-atmospheric pressure chemical ionization mass spectrometry.

PubMed

Tolrà, R P; Alonso, R; Poschenrieder, C; Barceló, D; Barceló, J

2000-08-11

Liquid chromatography-atmospheric pressure chemical ionization mass spectrometry was used to identify glucosinolates in plant extracts. Optimization of the analytical conditions and the determination of the method detection limit was performed using commercial 2-propenylglucosinolate (sinigrin). Optimal values for the following parameters were determined: nebulization pressure, gas temperature, flux of drying gas, capillar voltage, corona current and fragmentor conditions. The method detection limit for sinigrin was 2.85 ng. For validation of the method the glucosinolates in reference material (rapeseed) from the Community Bureau of Reference Materials (BCR) were analyzed. The method was applied for the determination of glucosinolates in Thlaspi caerulescens plants.

Ionization source utilizing a multi-capillary inlet and method of operation

DOEpatents

Smith, Richard D.; Kim, Taeman; Udseth, Harold R.

2004-10-12

A multi-capillary inlet to focus ions and other charged particles generated at or near atmospheric pressure into a relatively low pressure region, which allows increased conductance of ions and other charged particles. The multi-capillary inlet is juxtaposed between an ion source and the interior of an instrument maintained at near atmospheric pressure, it finds particular advantages when deployed to improve the ion transmission between an electrospray ionization source and the first vacuum stage of a mass spectrometer, and finds its greatest advantages when deployed in conjunction with an electrodynamic (RF) ion funnel deployed within the interior of the mass spectrometer, particularly an ion funnel equipped with a jet disturber.

Theoretical investigation of dielectric corona pre-ionization TEA nitrogen laser based on transmission line method

NASA Astrophysics Data System (ADS)

Bahrampour, Alireza; Fallah, Robabeh; Ganjovi, Alireza A.; Bahrampour, Abolfazl

2007-07-01

This paper models the dielectric corona pre-ionization, capacitor transfer type of flat-plane transmission line traveling wave transverse excited atmospheric pressure nitrogen laser by a non-linear lumped RLC electric circuit. The flat-plane transmission line and the pre-ionizer dielectric are modeled by a lumped linear RLC and time-dependent non-linear RC circuit, respectively. The main discharge region is considered as a time-dependent non-linear RLC circuit where its resistance value is also depends on the radiated pre-ionization ultra violet (UV) intensity. The UV radiation is radiated by the resistance due to the surface plasma on the pre-ionizer dielectric. The theoretical predictions are in a very good agreement with the experimental observations. The electric circuit equations (including the ionization rate equations), the equations of laser levels population densities and propagation equation of laser intensities, are solved numerically. As a result, the effects of pre-ionizer dielectric parameters on the electrical behavior and output laser intensity are obtained.

Leidenfrost phenomenon-assisted thermal desorption (LPTD) and its application to open ion sources at atmospheric pressure mass spectrometry.

PubMed

Saha, Subhrakanti; Chen, Lee Chuin; Mandal, Mridul Kanti; Hiraoka, Kenzo

2013-03-01

This work describes the development and application of a new thermal desorption technique that makes use of the Leidenfrost phenomenon in open ion sources at atmospheric pressure for direct mass spectrometric detection of ultratrace levels of illicit, therapeutic, and stimulant drugs, toxicants, and peptides (molecular weight above 1 kDa) in their unaltered state from complex real world samples without or with minor sample pretreatment. A low temperature dielectric barrier discharge ion source was used throughout the experiments and the analytical figures of merit of this technique were investigated. Further, this desorption technique coupled with other ionization sources such as electrospray ionization (ESI) and dc corona discharge atmospheric pressure chemical ionization (APCI) in open atmosphere was also investigated. The use of the high-resolution 'Exactive Orbitrap' mass spectrometer provided unambiguous identification of trace levels of the targeted compounds from complex mixtures and background noise; the limits of detection for various small organic molecules and peptides treated with this technique were at the level of parts per trillion and 10(-9) M, respectively. The high sensitivity of the present technique is attributed to the spontaneous enrichment of analyte molecules during the slow evaporation of the solvent, as well as to the sequential desorption of molecules from complex mixtures based on their volatilities. This newly developed desorption technique is simple and fast, while molecular ions are observed as the major ions.

Ultrafast quantum control of ionization dynamics in krypton.

PubMed

Hütten, Konrad; Mittermair, Michael; Stock, Sebastian O; Beerwerth, Randolf; Shirvanyan, Vahe; Riemensberger, Johann; Duensing, Andreas; Heider, Rupert; Wagner, Martin S; Guggenmos, Alexander; Fritzsche, Stephan; Kabachnik, Nikolay M; Kienberger, Reinhard; Bernhardt, Birgitta

2018-02-19

Ultrafast spectroscopy with attosecond resolution has enabled the real time observation of ultrafast electron dynamics in atoms, molecules and solids. These experiments employ attosecond pulses or pulse trains and explore dynamical processes in a pump-probe scheme that is selectively sensitive to electronic state of matter via photoelectron or XUV absorption spectroscopy or that includes changes of the ionic state detected via photo-ion mass spectrometry. Here, we demonstrate how the implementation of combined photo-ion and absorption spectroscopy with attosecond resolution enables tracking the complex multidimensional excitation and decay cascade of an Auger auto-ionization process of a few femtoseconds in highly excited krypton. In tandem with theory, our study reveals the role of intermediate electronic states in the formation of multiply charged ions. Amplitude tuning of a dressing laser field addresses different groups of decay channels and allows exerting temporal and quantitative control over the ionization dynamics in rare gas atoms.

Response of GaAs charge storage devices to transient ionizing radiation

NASA Astrophysics Data System (ADS)

Hetherington, D. L.; Klem, J. F.; Hughes, R. C.; Weaver, H. T.

Charge storage devices in which non-equilibrium depletion regions represent stored charge are sensitive to ionizing radiation. This results since the radiation generates electron-hole pairs that neutralize excess ionized dopant charge. Silicon structures, such as dynamic RAM or CCD cells are particularly sensitive to radiation since carrier diffusion lengths in this material are often much longer than the depletion width, allowing collection of significant quantities of charge from quasi-neutral sections of the device. For GaAs the situation is somewhat different in that minority carrier diffusion lengths are shorter than in silicon, and although mobilities are higher, we expect a reduction of radiation sensitivity as suggested by observations of reduced quantum efficiency in GaAs solar cells. Dynamic memory cells in GaAs have potential increased retention times. In this paper, we report the response of a novel GaAs dynamic memory element to transient ionizing radiation. The charge readout technique is nondestructive over a reasonable applied voltage range and is more sensitive to stored charge than a simple capacitor.

Gaseous toroid around Saturn. [Saturnian ring system for atomic hydrogen trapping in Titan atmospheric model

NASA Technical Reports Server (NTRS)

Mcdonough, T. R.

1974-01-01

The trapping of Titan's escaping atmosphere in the Saturnian system by a toroidal ring is discussed. The radius of the toroid is comparable to Titan's orbit, or about ten times larger than the visible rings. Theoretical atmospheric models are formulated that consider Saturn's gravitational attraction and magnetospheric properties in forming this toroid and in protecting toroid particles from direct ionization by solar wind particles.

Atmospheric Photooxidation Products and Chemistry of Current-use Pesticides

NASA Astrophysics Data System (ADS)

Murschell, T.; Farmer, D.

2017-12-01

Pesticides are widely used in agricultural, commercial, and residential applications across the United States. Pesticides can volatilize off targets and travel long distances, with atmospheric lifetimes determined by both physical and chemical loss processes. In particular, oxidation by the hydroxyl radical (OH) can reduce the lifetime and thus atmospheric transport of pesticides, though the rates and oxidation products of atmospheric pesticide oxidation are poorly understood. Here, we investigate reactions of current-use pesticides with OH. MCPA, triclopyr, and fluroxypyr are herbicides that are often formulated together to target broadleaf weeds. We detect these species in the gas-phase using real-time high resolution chemical ionization mass spectrometry (CIMS) with both acetate and iodide reagent ions. We used an Oxidative Flow Reactor to explore OH radical oxidation and photolysis of these compounds, simulating up to 5 equivalent days of atmospheric aging by OH. Use of two ionization schemes allowed for the more complete representation of the OH radical oxidation of the three pesticides. The high resolution mass spectra allows us to deduce structures of the oxidation products and identify multi-generational chemistry. In addition, we observe nitrogen oxides, as well as isocyanic acid (HNCO), from some nitrogen-containing pesticides. We present yields of species of atmospheric importance, including NOx and halogen species and consider their impact on air quality following pesticide application.

HO2 measurements at atmospheric concentrations using a chemical ionization mass spectrometry

NASA Astrophysics Data System (ADS)

Albrecht, S.; Novelli, A.; Hofzumahaus, A.; Kang, S.; Baker, Y.; Mentel, T. F.; Fuchs, H.

2017-12-01

Correct and precise measurements of atmospheric radical species are necessary for a better understanding of the oxidative capacity of the atmosphere. Due to the reactivity of radicals, and their consequent low concentrations, direct measurements of these species are particularly challenging and have been proven in the past to be affected by interfering species. Here we present a chemical ionization source coupled to an APi-HR-TOF-MS (Aerodyne Research Inc.), which has a limit of detection for HO2 radicals well below its atmospheric concentrations ( 1 x 108 molecules cm-3). The instrument was calibrated with a well-established and characterized HO2 calibration source in use for the laser induced fluorescence instrument in the Forschungszentrum Jülich. Within the source, a well characterized amount of HO2 radicals is produced after photolysis of water by a mercury lamp. In addition, several experiments were performed in the atmosphere simulation chamber SAPHIR at the Forschungszentrum Jülich to test for potential interferences. Measurements of HO2 radicals were concurrently detected by a laser induced fluorescence instrument allowing for the comparison of measurements within the two different and independent techniques for various atmospheric conditions regarding concentrations of O3, NOx and VOCs. Results from the intercomparison together with the calibration procedure of the instrument and laboratory characterization will be presented.

Martian Atmospheric Pressure Static Charge Elimination Tool

NASA Technical Reports Server (NTRS)

Johansen, Michael R.

2014-01-01

A Martian pressure static charge elimination tool is currently in development in the Electrostatics and Surface Physics Laboratory (ESPL) at NASA's Kennedy Space Center. In standard Earth atmosphere conditions, static charge can be neutralized from an insulating surface using air ionizers. These air ionizers generate ions through corona breakdown. The Martian atmosphere is 7 Torr of mostly carbon dioxide, which makes it inherently difficult to use similar methods as those used for standard atmosphere static elimination tools. An initial prototype has been developed to show feasibility of static charge elimination at low pressure, using corona discharge. A needle point and thin wire loop are used as the corona generating electrodes. A photo of the test apparatus is shown below. Positive and negative high voltage pulses are sent to the needle point. This creates positive and negative ions that can be used for static charge neutralization. In a preliminary test, a floating metal plate was charged to approximately 600 volts under Martian atmospheric conditions. The static elimination tool was enabled and the voltage on the metal plate dropped rapidly to -100 volts. This test data is displayed below. Optimization is necessary to improve the electrostatic balance of the static elimination tool.

AMS+ALS: Kinetic and Product Studies of the Heterogeneous Oxidation of Organic Aerosol at the Advanced Light Source

NASA Astrophysics Data System (ADS)

Kroll, J. H.; Wilson, K. R.; Kessler, S. H.; Browne, E. C.; Nah, T.; Smith, J.; Worsnop, D. R.

2014-12-01

The atmospheric oxidation of condensed-phase organic species can have a major influence on the composition, properties, and impacts of organic aerosol (OA); however the rates and products of such "aging" reactions are poorly constrained. Here we describe a series of laboratory experiments aimed at better understanding one class of aging reactions, the heterogeneous oxidation of OA by gas-phase oxidants. Central to these experiments is the availability of vacuum ultraviolet (VUV) light at the Chemical Dynamics Beamline of the Advanced Light Source at LBNL, which enables the implementation of VUV photoionization aerosol mass spectrometry. This technique allows for the real-time, speciated measurement of OA composition, yielding molecular information that is highly complementary to ensemble data from electron-impact ionization. OA composition is measured with both ionization schemes as a function of oxidant exposure within a flow reactor, providing detailed information on the kinetics and products of heterogeneous oxidation over multiple generations of oxidation. Specific topics investigated include the branching between functionalization and fragmentation of OA components, the formation of secondary organic aerosol from photolytically-generated radical species, and the heterogeneous aging of soot-associated organic species.

Assessing the sensitivity of benzene cluster cation chemical ionization mass spectrometry toward a wide array of biogenic volatile organic compounds

NASA Astrophysics Data System (ADS)

Lavi, Avi; Vermeuel, Michael; Novak, Gordon; Bertram, Timothy

2017-04-01

Chemical ionization mass spectrometry is a real-time, sensitive and selective measurement technique for the detection of volatile organic compounds (VOCs). The benefits of CIMS technology make it highly suitable for field measurements that requires fast (10Hz and higher) response rates, such as the study of surface-atmosphere exchange processes by the eddy covariance method. The use of benzene cluster cations as a regent ion was previously demonstrated as a sensitive and selective method for the detection of select biogenic VOCs (e.g. isoprene, monoterpenes and sesquiterpenes) [Kim et al., 2016; Leibrock and Huey, 2000]. Quantitative analysis of atmospheric trace gases necessitates calibration for each analyte as a function of atmospheric conditions. We describe a custom designed calibration system, based on liquid evaporation, for determination of the sensitivity of the benzene-CIMS to a wide range of organic compounds at atmospherically relevant mixing ratios (<200 ppt). We report on the effect of atmospheric water vapor and oxygen concentrations on instrument response for isoprene and a wide range of monoterpenes and sesquiterpenes. To gain mechanistic insight into the ion-molecule reactions and the role of water vapor and oxygen, we compare our measured sensitivities with a computational analysis of the charge distribution between the analyte, reagent ion and water molecules in the gas phase. These parameters provide insight on the ionization mechanism and provide parameters for quantification of organic molecules measured during field campaigns. References Kim, M. J., M. C. Zoerb, N. R. Campbell, K. J. Zimmermann, B. W. Blomquist, B. J. Huebert, and T. H. Bertram (2016), Revisiting benzene cluster cations for the chemical ionization of dimethyl sulfide and select volatile organic compounds, Atmos Meas Tech, 9(4), 1473-1484, doi:10.5194/amt-9-1473-2016. Leibrock, E., and L. G. Huey (2000), Ion chemistry for the detection of isoprene and other volatile organic compounds in ambient air, Geophys Res Lett, 27(12), 1719-1722, doi:Doi 10.1029/1999gl010804.

Quantitative measurement of electron number in nanosecond and picosecond laser-induced air breakdown

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Yue; Sawyer, Jordan C.; Su, Liu

2016-05-07

Here we present quantitative measurements of total electron numbers in laser-induced air breakdown at pressures ranging from atmospheric to 40 bar{sub g} by 10 ns and 100 ps laser pulses. A quantifiable definition for the laser-induced breakdown threshold is identified by a sharp increase in the measurable total electron numbers via dielectric-calibrated coherent microwave scattering. For the 10 ns laser pulse, the threshold of laser-induced breakdown in atmospheric air is defined as the total electron number of ∼10{sup 6}. This breakdown threshold decreases with an increase of pressure and laser photon energy (shorter wavelength), which is consistent with the theory of initialmore » multiphoton ionization and subsequent avalanche processes. For the 100 ps laser pulse cases, a clear threshold is not present and only marginal pressure effects can be observed, which is due to the short pulse duration leading to stronger multiphoton ionization and minimal collisional avalanche ionization.« less

Laser Microdissection and Atmospheric Pressure Chemical Ionization Mass Spectrometry Coupled for Multimodal Imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lorenz, Matthias; Ovchinnikova, Olga S; Kertesz, Vilmos

2013-01-01

This paper describes the coupling of ambient laser ablation surface sampling, accomplished using a laser capture microdissection system, with atmospheric pressure chemical ionization mass spectrometry for high spatial resolution multimodal imaging. A commercial laser capture microdissection system was placed in close proximity to a modified ion source of a mass spectrometer designed to allow for sampling of laser ablated material via a transfer tube directly into the ionization region. Rhodamine 6G dye of red sharpie ink in a laser etched pattern as well as cholesterol and phosphatidylcholine in a cerebellum mouse brain thin tissue section were identified and imaged frommore » full scan mass spectra. A minimal spot diameter of 8 m was achieved using the 10X microscope cutting objective with a lateral oversampling pixel resolution of about 3.7 m. Distinguishing between features approximately 13 m apart in a cerebellum mouse brain thin tissue section was demonstrated in a multimodal fashion including co-registered optical and mass spectral chemical images.« less

Gas Chromatography/Atmospheric Pressure Chemical Ionization-Fourier Transform Ion Cyclotron Resonance Mass Spectrometry of Pyrolysis Oil from German Brown Coal

PubMed Central

Zuber, Jan; Kroll, Marius M.; Rathsack, Philipp; Otto, Matthias

2016-01-01

Pyrolysis oil from the slow pyrolysis of German brown coal from Schöningen, obtained at a temperature of 500°C, was separated and analyzed using hyphenation of gas chromatography with an atmospheric pressure chemical ionization source operated in negative ion mode and Fourier transform ion cyclotron resonance mass spectrometry (GC-APCI-FT-ICR-MS). Development of this ultrahigh-resolving analysis method is described, that is, optimization of specific GC and APCI parameters and performed data processing. The advantages of GC-APCI-FT-ICR-MS hyphenation, for example, soft ionization, ultrahigh-resolving detection, and most important isomer separation, were demonstrated for the sample liquid. For instance, it was possible to separate and identify nine different propylphenol, ethylmethylphenol, and trimethylphenol isomers. Furthermore, homologous series of different acids, for example, alkyl and alkylene carboxylic acids, were verified, as well as homologous series of alkyl phenols, alkyl dihydroxy benzenes, and alkoxy alkyl phenols. PMID:27066076

Assessment of Real-Time Time-Dependent Density Functional Theory (RT-TDDFT) in Radiation Chemistry: Ionized Water Dimer.

PubMed

Chalabala, Jan; Uhlig, Frank; Slavíček, Petr

2018-03-29

Ionization in the condensed phase and molecular clusters leads to a complicated chain of processes with coupled electron-nuclear dynamics. It is difficult to describe such dynamics with conventional nonadiabatic molecular dynamics schemes since the number of states swiftly increases as the molecular system grows. It is therefore attractive to use a direct electron and nuclear propagation such as the real-time time-dependent density functional theory (RT-TDDFT). Here we report a RT-TDDFT benchmark study on simulations of singly and doubly ionized states of a water monomer and dimer as a prototype for more complex processes in a condensed phase. We employed the RT-TDDFT based Ehrenfest molecular dynamics with a generalized gradient approximate (GGA) functional and compared it with wave-function-based surface hopping (SH) simulations. We found that the initial dynamics of a singly HOMO ionized water dimer is similar for both the RT-TDDFT/GGA and the SH simulations but leads to completely different reaction channels on a longer time scale. This failure is attributed to the self-interaction error in the GGA functionals and it can be avoided by using hybrid functionals with large fraction of exact exchange (represented here by the BHandHLYP functional). The simulations of doubly ionized states are reasonably described already at the GGA level. This suggests that the RT-TDDFT/GGA method could describe processes following the autoionization processes such as Auger emission, while its applicability to more complex processes such as intermolecular Coulombic decay remains limited.

Fast transient analysis and first-stage collision-induced dissociation with the flowing atmospheric-pressure afterglow ionization source to improve analyte detection and identification.

PubMed

Shelley, Jacob T; Hieftje, Gary M

2010-04-01

The recent development of ambient desorption/ionization mass spectrometry (ADI-MS) has enabled fast, simple analysis of many different sample types. The ADI-MS sources have numerous advantages, including little or no required sample pre-treatment, simple mass spectra, and direct analysis of solids and liquids. However, problems of competitive ionization and limited fragmentation require sample-constituent separation, high mass accuracy, and/or tandem mass spectrometry (MS/MS) to detect, identify, and quantify unknown analytes. To maintain the inherent high throughput of ADI-MS, it is essential for the ion source/mass analyzer combination to measure fast transient signals and provide structural information. In the current study, the flowing atmospheric-pressure afterglow (FAPA) ionization source is coupled with a time-of-flight mass spectrometer (TOF-MS) to analyze fast transient signals (<500 ms FWHM). It was found that gas chromatography (GC) coupled with the FAPA source resulted in a reproducible (<5% RSD) and sensitive (detection limits of <6 fmol for a mixture of herbicides) system with analysis times of ca. 5 min. Introducing analytes to the FAPA in a transient was also shown to significantly reduce matrix effects caused by competitive ionization by minimizing the number and amount of constituents introduced into the ionization source. Additionally, MS/MS with FAPA-TOF-MS, enabling analyte identification, was performed via first-stage collision-induced dissociation (CID). Lastly, molecular and structural information was obtained across a fast transient peak by modulating the conditions that caused the first-stage CID.

Vortex focusing of ions produced in corona discharge.

PubMed

Kolomiets, Yuri N; Pervukhin, Viktor V

2013-06-15

Completeness of the ion transportation into an analytical path defines the efficiency of ionization analysis techniques. This is of particular importance for atmospheric pressure ionization sources like corona discharge, electrospray, ionization with radioactive ((3)H, (63)Ni) isotopes that produce nonuniform spatial distribution of sample ions. The available methods of sample ion focusing are either efficient at reduced pressure (~1Torr) or feature high sample losses. This paper deals with experimental research into atmospheric pressure focusing of unipolar (positive) ions using a highly swirled air stream with a well-defined vortex core. Effects of electrical fields from corona needle and inlet capillary of mass spectrometer on collection efficiency is considered. We used a corona discharge to produce an ionized unipolar sample. It is shown experimentally that with an electrical field barrier efficient transportation and focusing of an ionized sample are possible only when a metal plate restricting the stream and provided with an opening covered with a grid is used. This gives a five-fold increase of the transportation efficiency. It is shown that the electric field barrier in the vortex sampling region reduces the efficiency of remote ionized sample transportation two times. The difference in the efficiency of light ion focusing observed may be explained by a high mobility and a significant effect of the electric field barrier upon them. It is possible to conclude based on the experimental data that the presence of the field barrier narrows considerably (more than by one and half) the region of the vortex sample ion focusing. Copyright © 2013 Elsevier B.V. All rights reserved.

Two-dimensional Radiative Magnetohydrodynamic Simulations of Partial Ionization in the Chromosphere. II. Dynamics and Energetics of the Low Solar Atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Martínez-Sykora, Juan; Pontieu, Bart De; Hansteen, Viggo H.

2017-09-20

We investigate the effects of interactions between ions and neutrals on the chromosphere and overlying corona using 2.5D radiative MHD simulations with the Bifrost code. We have extended the code capabilities implementing ion–neutral interaction effects using the generalized Ohm’s law, i.e., we include the Hall term and the ambipolar diffusion (Pedersen dissipation) in the induction equation. Our models span from the upper convection zone to the corona, with the photosphere, chromosphere, and transition region partially ionized. Our simulations reveal that the interactions between ionized particles and neutral particles have important consequences for the magnetothermodynamics of these modeled layers: (1) ambipolarmore » diffusion increases the temperature in the chromosphere; (2) sporadically the horizontal magnetic field in the photosphere is diffused into the chromosphere, due to the large ambipolar diffusion; (3) ambipolar diffusion concentrates electrical currents, leading to more violent jets and reconnection processes, resulting in (3a) the formation of longer and faster spicules, (3b) heating of plasma during the spicule evolution, and (3c) decoupling of the plasma and magnetic field in spicules. Our results indicate that ambipolar diffusion is a critical ingredient for understanding the magnetothermodynamic properties in the chromosphere and transition region. The numerical simulations have been made publicly available, similar to previous Bifrost simulations. This will allow the community to study realistic numerical simulations with a wider range of magnetic field configurations and physics modules than previously possible.« less

Two-dimensional Radiative Magnetohydrodynamic Simulations of Partial Ionization in the Chromosphere. II. Dynamics and Energetics of the Low Solar Atmosphere

NASA Astrophysics Data System (ADS)

Martínez-Sykora, Juan; De Pontieu, Bart; Carlsson, Mats; Hansteen, Viggo H.; Nóbrega-Siverio, Daniel; Gudiksen, Boris V.

2017-09-01

We investigate the effects of interactions between ions and neutrals on the chromosphere and overlying corona using 2.5D radiative MHD simulations with the Bifrost code. We have extended the code capabilities implementing ion-neutral interaction effects using the generalized Ohm’s law, I.e., we include the Hall term and the ambipolar diffusion (Pedersen dissipation) in the induction equation. Our models span from the upper convection zone to the corona, with the photosphere, chromosphere, and transition region partially ionized. Our simulations reveal that the interactions between ionized particles and neutral particles have important consequences for the magnetothermodynamics of these modeled layers: (1) ambipolar diffusion increases the temperature in the chromosphere; (2) sporadically the horizontal magnetic field in the photosphere is diffused into the chromosphere, due to the large ambipolar diffusion; (3) ambipolar diffusion concentrates electrical currents, leading to more violent jets and reconnection processes, resulting in (3a) the formation of longer and faster spicules, (3b) heating of plasma during the spicule evolution, and (3c) decoupling of the plasma and magnetic field in spicules. Our results indicate that ambipolar diffusion is a critical ingredient for understanding the magnetothermodynamic properties in the chromosphere and transition region. The numerical simulations have been made publicly available, similar to previous Bifrost simulations. This will allow the community to study realistic numerical simulations with a wider range of magnetic field configurations and physics modules than previously possible.

One-Dimensional Hybrid Satellite Track Model for the Dynamics Explorer 2 (DE 2) Satellite

NASA Technical Reports Server (NTRS)

Deng, Wei; Killeen, T. L.; Burns, A. G.; Johnson, R. M.; Emery, B. A.; Roble, R. G.; Winningham, J. D.; Gary, J. B.

1995-01-01

A one-dimensional hybrid satellite track model has been developed to calculate the high-latitude thermospheric/ionospheric structure below the satellite altitude using Dynamics Explorer 2 (DE 2) satellite measurements and theory. This model is based on Emery et al. satellite track code but also includes elements of Roble et al. global mean thermosphere/ionosphere model. A number of parameterizations and data handling techniques are used to input satellite data from several DE 2 instruments into this model. Profiles of neutral atmospheric densities are determined from the MSIS-90 model and measured neutral temperatures. Measured electron precipitation spectra are used in an auroral model to calculate particle impact ionization rates below the satellite. These rates are combined with a solar ionization rate profile and used to solve the O(+) diffusion equation, with the measured electron density as an upper boundary condition. The calculated O(+) density distribution, as well as the ionization profiles, are then used in a photochemical equilibrium model to calculate the electron and molecular ion densities. The electron temperature is also calculated by solving the electron energy equation with an upper boundary condition determined by the DE 2 measurement. The model enables calculations of altitude profiles of conductivity and Joule beating rate along and below the satellite track. In a first application of the new model, a study is made of thermospheric and ionospheric structure below the DE 2 satellite for a single orbit which occurred on October 25, 1981. The field-aligned Poynting flux, which is independently obtained for this orbit, is compared with the model predictions of the height-integrated energy conversion rate. Good quantitative agreement between these two estimates has been reached. In addition, measurements taken at the incoherent scatter radar site at Chatanika (65.1 deg N, 147.4 deg W) during a DE 2 overflight are compared with the model calculations. A good agreement was found in lower thermospheric conductivities and Joule heating rate.

Nitrogen-Containing Low Volatile Compounds from Pinonaldehyde-Dimethylamine Reaction in the Atmosphere: A Laboratory and Field Study.

PubMed

Duporté, Geoffroy; Parshintsev, Jevgeni; Barreira, Luís M F; Hartonen, Kari; Kulmala, Markku; Riekkola, Marja-Liisa

2016-05-03

Pinonaldehyde, which is among the most abundant oxidation products of α-pinene, and dimethylamine were selected to study the formation of N-containing low volatile compounds from aldehyde-amine reactions in the atmosphere. Gas phase reactions took place in a Tedlar bag, which was connected to a mass spectrometer ionization source via a short deactivated fused silica column. In addition to on-line analysis, abundance of gaseous precursors and reaction products were monitored off-line. Condensable products were extracted from the bag's walls with a suitable solvent and analyzed by gas chromatography coupled to chemical ionization high-resolution quadrupole time-of-flight mass spectrometry and by ultra-high-performance liquid chromatography coupled to electrospray ionization Orbitrap mass spectrometry. The reactions carried out resulted in several mid-low vapor pressure nitrogen-containing compounds that are potentially important for the formation of secondary organic aerosols in the atmosphere. Further, the presence of brown carbon, confirmed by liquid chromatography-UV-vis-mass spectrometry, was observed. Some of the compounds identified in the laboratory study were also observed in aerosol samples collected at SMEAR II station (Hyytiälä, Finland) in August 2015 suggesting the importance of aldehyde-amine reactions for the aerosol formation and growth.

Alternating current corona discharge/atmospheric pressure chemical ionization for mass spectrometry.

PubMed

Habib, Ahsan; Usmanov, Dilshadbek; Ninomiya, Satoshi; Chen, Lee Chuin; Hiraoka, Kenzo

2013-12-30

Although alternating current (ac) corona discharge has been widely used in the fields of material science and technology, no reports have been published on its application to an atmospheric pressure chemical ionization (APCI) ion source. In this work, ac corona discharge for an APCI ion source has been examined for the first time. The ambient atmospheric pressure ac corona discharge (15 kHz, 2.6 kVptp ) was generated by using a stainless steel acupuncture needle. The generated ions were measured using an ion trap mass spectrometer. A comparative study on ac and direct current (dc) corona APCI ion sources was carried out using triacetone triperoxide and trinitrotoluene as test samples. The ac corona discharge gave ion signals as strong as dc corona discharge for both positive and negative ion modes. In addition, softer ionization was obtained with ac corona discharge than with dc corona discharge. The erosion of the needle tip induced by ac corona was less than that obtained with positive mode dc corona. A good 'yardstick' for assessing ac corona is that it can be used for both positive and negative ion modes without changing the polarity of the high-voltage power supply. Thus, ac corona can be an alternative to conventional dc corona for APCI ion sources. Copyright © 2013 John Wiley & Sons, Ltd.

High pressure xenon ionization detector

DOEpatents

Markey, J.K.

1989-11-14

A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0 to 30 C. 2 figs.

High pressure xenon ionization detector

DOEpatents

Markey, John K.

1989-01-01

A method is provided for detecting ionization comprising allowing particles that cause ionization to contact high pressure xenon maintained at or near its critical point and measuring the amount of ionization. An apparatus is provided for detecting ionization, the apparatus comprising a vessel containing a ionizable medium, the vessel having an inlet to allow high pressure ionizable medium to enter the vessel, a means to permit particles that cause ionization of the medium to enter the vessel, an anode, a cathode, a grid and a plurality of annular field shaping rings, the field shaping rings being electrically isolated from one another, the anode, cathode, grid and field shaping rings being electrically isolated from one another in order to form an electric field between the cathode and the anode, the electric field originating at the anode and terminating at the cathode, the grid being disposed between the cathode and the anode, the field shaping rings being disposed between the cathode and the grid, the improvement comprising the medium being xenon and the vessel being maintained at a pressure of 50 to 70 atmospheres and a temperature of 0.degree. to 30.degree. C.

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

DOE PAGES

Hu, S. X.; Collins, Lee A.; Goncharov, V. N.; ...

2016-04-14

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations on the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm 3 and T = 15,625 to 500,000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which exhibits the correct behaviors of continuum lowering and pressure ionization. The thermal conductivities (κ QMD) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted withmore » a generalized Coulomb logarithm [(lnΛ) QMD] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Furthermore, hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted –20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.« less

Proton transfer mediated by the vibronic coupling in oxygen core ionized states of glyoxalmonoxime studied by infrared-X-ray pump-probe spectroscopy.

PubMed

Felicíssimo, V C; Guimarães, F F; Cesar, A; Gel'mukhanov, F; Agren, H

2006-11-30

The theory of IR-X-ray pump-probe spectroscopy beyond the Born-Oppenheimer approximation is developed and applied to the study of the dynamics of intramolecular proton transfer in glyoxalmonoxime leading to the formation of the tautomer 2-nitrosoethenol. Due to the IR pump pulses the molecule gains sufficient energy to promote a proton to a weakly bound well. A femtosecond X-ray pulse snapshots the wave packet route and, hence, the dynamics of the proton transfer. The glyoxalmonoxime molecule contains two chemically nonequivalent oxygen atoms that possess distinct roles in the hydrogen bond, a hydrogen donor and an acceptor. Core ionizations of these form two intersecting core-ionized states, the vibronic coupling between which along the OH stretching mode partially delocalizes the core hole, resulting in a hopping of the core hole from one site to another. This, in turn, affects the dynamics of the proton transfer in the core-ionized state. The quantum dynamical simulations of X-ray photoelectron spectra of glyoxalmonoxime driven by strong IR pulses demonstrate the general applicability of the technique for studies of intramolecular proton transfer in systems with vibronic coupling.

Time-dependent quantum chemistry of laser driven many-electron molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen-Dang, Thanh-Tung; Couture-Bienvenue, Étienne; Viau-Trudel, Jérémy

2014-12-28

A Time-Dependent Configuration Interaction approach using multiple Feshbach partitionings, corresponding to multiple ionization stages of a laser-driven molecule, has recently been proposed [T.-T. Nguyen-Dang and J. Viau-Trudel, J. Chem. Phys. 139, 244102 (2013)]. To complete this development toward a fully ab-initio method for the calculation of time-dependent electronic wavefunctions of an N-electron molecule, we describe how tools of multiconfiguration quantum chemistry such as the management of the configuration expansion space using Graphical Unitary Group Approach concepts can be profitably adapted to the new context, that of time-resolved electronic dynamics, as opposed to stationary electronic structure. The method is applied tomore » calculate the detailed, sub-cycle electronic dynamics of BeH{sub 2}, treated in a 3–21G bound-orbital basis augmented by a set of orthogonalized plane-waves representing continuum-type orbitals, including its ionization under an intense λ = 800 nm or λ = 80 nm continuous-wave laser field. The dynamics is strongly non-linear at the field-intensity considered (I ≃ 10{sup 15} W/cm{sup 2}), featuring important ionization of an inner-shell electron and strong post-ionization bound-electron dynamics.« less

Design of a secondary ionization target for direct production of a C- beam from CO2 pulses for online AMS.

PubMed

Salazar, Gary; Ognibene, Ted

2013-01-01

We designed and optimized a novel device "target" that directs a CO 2 gas pulse onto a Ti surface where a Cs + beam generates C - from the CO 2 . This secondary ionization target enables an accelerator mass spectrometer to ionize pulses of CO 2 in the negative mode to measure 14 C/ 12 C isotopic ratios in real time. The design of the targets were based on computational flow dynamics, ionization mechanism and empirical optimization. As part of the ionization mechanism, the adsorption of CO 2 on the Ti surface was fitted with the Jovanovic-Freundlich isotherm model using empirical and simulation data. The inferred adsorption constants were in good agreement with other works. The empirical optimization showed that amount of injected carbon and the flow speed of the helium carrier gas improve the ionization efficiency and the amount of 12 C - produced until reaching a saturation point. Linear dynamic range between 150 and 1000 ng of C and optimum carrier gas flow speed of around 0.1 mL/min were shown. It was also shown that the ionization depends on the area of the Ti surface and Cs + beam cross-section. A range of ionization efficiency of 1-2.5% was obtained by optimizing the described parameters.

Chemistry and dynamics of the lower ionosphere of Mars

NASA Astrophysics Data System (ADS)

Haider, Syed A.; Sheel, Varun

MIRI: Validation and Testing Requirements The high energy cosmic rays propagate through the Martian atmosphere producing nucleonic cascades. The impact of primary cosmic rays onto the atmospheric gases produces protons, neutrons and pions. The neutral pions quickly decay to gamma rays and their contribution to energy deposition is very important in the lower atmosphere of Mars. Near the mesosphere, the maximum ion production rates are controlled by protons. The charged pions decay to meons, which do not decay and their energy is transferred to the surface on reaching the ground. In this paper we have calculated production rates, conductivity, densities of positive and negative ions due to cosmic ray ionization. The model couples ion-neutral, electron neutral, dissociation of positive and negative ions, electron detachment, ion-ion and ion-electron recombination processes. The hydrated hydronium and water cluster ions (H _{3}O (+) (H _{2}O) _{n} , NO _{2} (-) (H _{2}O) _{n} and CO _{3} (-) (H _{2}O) _{n} for n=1-4) are dominated below 60 km, while NO (+) and O _{2} (+) are major ions above this altitude. We have also examined the effect of dust storms on the lower ionosphere of Mars. It is found that during intense period of dust storms, the D region ionosphere disappears for several weeks until the dust settles down to its normal condition

Nostradamus: The radar that wanted to be a seismometer

NASA Astrophysics Data System (ADS)

Occhipinti, Giovanni; Dorey, Philippe; Farges, Thomas; Lognonné, Philippe

2010-09-01

Surface waves emitted after large earthquakes are known to induce, by dynamic coupling, atmospheric infrasonic waves propagating upward through the neutral and ionized atmosphere. Those waves have been detected in the past at ionospheric heights using a variety of techniques, such as HF Doppler sounding or GPS receivers. The HF Doppler technique, particularly sensitive to the ionospheric signature of Rayleigh waves is used here to show ionospheric perturbations consistent with the propagation of Rayleigh wave phases R1 and R2 following the Sumatra earthquake on the 28 March 2005 (M = 8.6). This is in our knowledge the first time that the phase R2 is detected by ionospheric sounding. In addition, we prove here that the ionospheric signature of R2 is also observed by over-the-horizon (OTH) Radar. The latter was never used before to detect seismic signature in the ionosphere. Adding the OTH Radar to the list of the “ionospheric seismometers” we discuss and compare the performances of the three different instruments mentioned above, namely HF Doppler sounding, GPS receivers and OTH radar.

Smaller solar system bodies and orbits; Proceedings of Symposium 3, Workshops II, III, and XXVI, and Topical Meetings of the 27th COSPAR Plenary Meeting, Espoo, Finland, July 18-29, 1988

NASA Technical Reports Server (NTRS)

Runcorn, S. K. (Editor); Carr, M. H. (Editor); Moehlmann, D. (Editor); Stiller, H. (Editor); Matson, D. L. (Editor); Ambrosius, B. A. C. (Editor); Kessler, D. J. (Editor)

1990-01-01

Topics discussed in this volume include the reappraisal of the moon and Mars/Phobos/Deimos; the origin and evolution of planetary and satellite systems; asteroids, comets, and dust (a post-IRAS perspective); satellite dynamics; future planetary missions; and orbital debris. Papers are presented on a comparison of the chemistry of moon and Mars, the use of a mobile surface radar to study the atmosphere and ionosphere, and laser-ionization studies with the technical models of the LIMA-D/Phobos. Attention is given to planetogonic scenarios and the evolution of relatively mass-rich preplanetary disks, the kinetic behavior of planetesimals revolving around the sun, the planetary evolution of Mars, and pre- and post-IRAS asteroid taxonomies. Consideration is also given to ocean tides and tectonic plate motions in high-precision orbit determination, the satellite altimeter calibration techniques, a theory of the motion of an artificial satellite in the earth atmosphere, ESA plans for planetary exploration, and the detection of earth orbiting objects by IRAS.

Microchip and wedge ion funnels and planar ion beam analyzers using same

DOEpatents

Shvartsburg, Alexandre A; Anderson, Gordon A; Smith, Richard D

2012-10-30

Electrodynamic ion funnels confine, guide, or focus ions in gases using the Dehmelt potential of oscillatory electric field. New funnel designs operating at or close to atmospheric gas pressure are described. Effective ion focusing at such pressures is enabled by fields of extreme amplitude and frequency, allowed in microscopic gaps that have much higher electrical breakdown thresholds in any gas than the macroscopic gaps of present funnels. The new microscopic-gap funnels are useful for interfacing atmospheric-pressure ionization sources to mass spectrometry (MS) and ion mobility separation (IMS) stages including differential IMS or FAIMS, as well as IMS and MS stages in various configurations. In particular, "wedge" funnels comprising two planar surfaces positioned at an angle and wedge funnel traps derived therefrom can compress ion beams in one dimension, producing narrow belt-shaped beams and laterally elongated cuboid packets. This beam profile reduces the ion density and thus space-charge effects, mitigating the adverse impact thereof on the resolving power, measurement accuracy, and dynamic range of MS and IMS analyzers, while a greater overlap with coplanar light or particle beams can benefit spectroscopic methods.

Smaller solar system bodies and orbits; Proceedings of Symposium 3, Workshops II, III, and XXVI, and Topical Meetings of the 27th COSPAR Plenary Meeting, Espoo, Finland, July 18-29, 1988

NASA Astrophysics Data System (ADS)

Runcorn, S. K.; Carr, M. H.; Moehlmann, D.; Stiller, H.; Matson, D. L.; Ambrosius, B. A. C.; Kessler, D. J.

Topics discussed in this volume include the reappraisal of the moon and Mars/Phobos/Deimos; the origin and evolution of planetary and satellite systems; asteroids, comets, and dust (a post-IRAS perspective); satellite dynamics; future planetary missions; and orbital debris. Papers are presented on a comparison of the chemistry of moon and Mars, the use of a mobile surface radar to study the atmosphere and ionosphere, and laser-ionization studies with the technical models of the LIMA-D/Phobos. Attention is given to planetogonic scenarios and the evolution of relatively mass-rich preplanetary disks, the kinetic behavior of planetesimals revolving around the sun, the planetary evolution of Mars, and pre- and post-IRAS asteroid taxonomies. Consideration is also given to ocean tides and tectonic plate motions in high-precision orbit determination, the satellite altimeter calibration techniques, a theory of the motion of an artificial satellite in the earth atmosphere, ESA plans for planetary exploration, and the detection of earth orbiting objects by IRAS.

Quantum Computational Calculations of the Ionization Energies of Acidic and Basic Amino Acids: Aspartate, Glutamate, Arginine, Lysine, and Histidine

NASA Astrophysics Data System (ADS)

de Guzman, C. P.; Andrianarijaona, M.; Lee, Y. S.; Andrianarijaona, V.

An extensive knowledge of the ionization energies of amino acids can provide vital information on protein sequencing, structure, and function. Acidic and basic amino acids are unique because they have three ionizable groups: the C-terminus, the N-terminus, and the side chain. The effects of multiple ionizable groups can be seen in how Aspartate's ionizable side chain heavily influences its preferred conformation (J Phys Chem A. 2011 April 7; 115(13): 2900-2912). Theoretical and experimental data on the ionization energies of many of these molecules is sparse. Considering each atom of the amino acid as a potential departing site for the electron gives insight on how the three ionizable groups affect the ionization process of the molecule and the dynamic coupling between the vibrational modes. In the following study, we optimized the structure of each acidic and basic amino acid then exported the three dimensional coordinates of the amino acids. We used ORCA to calculate single point energies for a region near the optimized coordinates and systematically went through the x, y, and z coordinates of each atom in the neutral and ionized forms of the amino acid. With the calculations, we were able to graph energy potential curves to better understand the quantum dynamic properties of the amino acids. The authors thank Pacific Union College Student Association for providing funds.

38 CFR 3.311 - Claims based on exposure to ionizing radiation.

Code of Federal Regulations, 2013 CFR

2013-07-01

... body in the field of health physics, nuclear medicine or radiology and if based on analysis of the... follows: (i) Atmospheric nuclear weapons test participation claims. In claims based upon participation in atmospheric nuclear testing, dose data will in all cases be requested from the appropriate office of the...

38 CFR 3.311 - Claims based on exposure to ionizing radiation.

Code of Federal Regulations, 2014 CFR

2014-07-01

... body in the field of health physics, nuclear medicine or radiology and if based on analysis of the... follows: (i) Atmospheric nuclear weapons test participation claims. In claims based upon participation in atmospheric nuclear testing, dose data will in all cases be requested from the appropriate office of the...

38 CFR 3.311 - Claims based on exposure to ionizing radiation.

Code of Federal Regulations, 2012 CFR

2012-07-01

... body in the field of health physics, nuclear medicine or radiology and if based on analysis of the... follows: (i) Atmospheric nuclear weapons test participation claims. In claims based upon participation in atmospheric nuclear testing, dose data will in all cases be requested from the appropriate office of the...

Atmospheric Ionizing Radiation and the High Speed Civil Transport. Chapter 1

NASA Technical Reports Server (NTRS)

Maiden, D. L.; Wilson, J. W.; Jones, I. W.; Goldhagen, P.

2003-01-01

Atmospheric ionizing radiation is produced by extraterrestrial radiations incident on the Earth's atmosphere. These extraterrestrial radiations are of two sources: ever present galactic cosmic rays with origin outside the solar system and transient solar particle events that are at times very intense events associated with solar activity lasting several hours to a few days. Although the galactic radiation penetrating through the atmosphere to the ground is low in intensity, the intensity is more than two orders of magnitude greater at commercial aircraft altitudes. The radiation levels at the higher altitudes of the High Speed Civil Transport (HSCT) are an additional factor of two higher. Ionizing radiation produces chemically active radicals in biological tissues that alter the cell function or result in cell death. Protection standards against low levels of ionizing radiation are based on limitation of excess cancer mortality or limitation of developmental injury resulting in permanent damage to the offspring during pregnancy. The crews of commercial air transport operations are considered as radiation workers by the EPA, the FAA, and the International Commission on Radiological Protection (ICRP). The annual exposures of aircrews depend on the latitudes and altitudes of operation and flight time. Flight hours have significantly increased since deregulation of the airline industry in the 1980's. The FAA estimates annual subsonic aircrew exposures to range from 0.2 to 9.1 mSv compared to 0.5 mSv exposure of the average nuclear power plant worker in the nuclear industry. The commercial aircrews of the HSCT may receive exposures above recently recommended allowable limits for even radiation workers if flying their allowable number of flight hours. An adequate protection philosophy for background exposures in HSCT commercial airtraffic cannot be developed at this time due to current uncertainty in environmental levels. In addition, if a large solar particle event occurs during flight at HSCT altitudes then passengers and crew may greatly exceed allowable limits unless means are available to reduce exposures.

VUV photodynamics of free tholins nanoparticles investigated by imaging Angle-Resolved Photoemission with the Synchrotron Radiation

NASA Astrophysics Data System (ADS)

Tigrine, Sarah; Nahon, Laurent; Carrasco, Nathalie; Garcia-Macias, Gustavo

2016-06-01

Thanks to the Cassini Huygens mission, it is now established that the aerosols appear from an altitude of 1,000 km in Titan's atmosphere. Once they are formed and through their descent towards the surface, those grains will still interact with persistent UV/VUV radiations, at different energies, that can reach lower atmospheric layers. This interaction has some impact, for example on the radiative transfer or on the ionization yield of the atmospheric compounds. Models are a good way to study those processes, but the lack of data on the refractive index or the absolute absorption/ionization cross subsections of the aerosols can be an obstacle. In order to shed some light and quantify those processes, we ionize analogs of aerosols produced with the PAMPRE experiment (LATMOS) on the SAPHIRS platform from the DESIRS VUV beamline at the synchrotron SOLEIL, equipped with an aerodynamic lens. The aerosols are injected directly under vacuum as isolated free nanoparticles and do not need to take the form of a film deposited on a substrate. The generated photoelectrons are then collected with a Velocity Map Imaging detector and their energetic and angular signatures are analyzed using the ARPES method (Angle-Resolved PhotoElectron Spectroscopy). Both the nanoparticles size distribution and the incident wavelength determine the parameters governing the photoemission process (intra-particles electron mean free path, photon penetration depth) as revealed by the angular distribution of the photoelectron showing in same cases a marked forward/backward asymmetry with respect to the photon axis. Those parameters may provide us with information on the optical behavior of the aerosols. In addition we can extract the ionization potential in direct connection with the absorption cross subsections of the aerosol, from which altitude dependent photodynamics can be unraveled. We will present here the experiments performed, at different VUV energies, on Titan's aerosol analogs with the ARPES method and show how the first results can have implications regarding Titan's atmosphere overall optical characteristics.

Selectivity of Electronic Coherence and Attosecond Ionization Delays in Strong-Field Double Ionization

NASA Astrophysics Data System (ADS)

Kobayashi, Yuki; Reduzzi, Maurizio; Chang, Kristina F.; Timmers, Henry; Neumark, Daniel M.; Leone, Stephen R.

2018-06-01

Experiments are presented on real-time probing of coherent electron dynamics in xenon initiated by strong-field double ionization. Attosecond transient absorption measurements allow for characterization of electronic coherences as well as relative ionization timings in multiple electronic states of Xe+ and Xe2 + . A high degree of coherence g =0.4 is observed between P3 2 0-P3 0 0 of Xe2 + , whereas for other possible pairs of states the coherences are below the detection limits of the experiments. A comparison of the experimental results with numerical simulations based on an uncorrelated electron-emission model shows that the coherences produced by strong-field double ionization are more selective than predicted. Surprisingly short ionization time delays, 0.85 fs, 0.64 fs, and 0.75 fs relative to Xe+ formation, are also measured for the P2 3 , P0 3 , and P1 3 states of Xe2 + , respectively. Both the unpredicted selectivity in the formation of coherence and the subfemtosecond time delays of specific states provide new insight into correlated electron dynamics in strong-field double ionization.

Communications Blackout Prediction for Atmospheric Entry of Mars Science Laboratory

NASA Technical Reports Server (NTRS)

Morabito, David; Edquist, Karl

2005-01-01

When a supersonic spacecraft enters a planetary atmosphere with v >> v(sub sound), a shock layer forms in the front of the body. An ionized sheath of plasma develops around the spacecraft, which results from the ionization of the atmospheric constituents as they are compressed and heated by the shock or heated within the boundary layer next to the surface. When the electron density surrounding the spacecraft becomes sufficiently high, communications can be disrupted (attenuation/blackout). During Mars Science Laboratory's (MSL's) atmospheric entry there will likely be a communication outage due to charged particles on the order of 60 to 100 seconds using a UHF link frequency looking out the shoulders of the wake region to orbiting relay asset. A UHF link looking out the base region would experience a shorter duration blackout, about 35 seconds for the stressed trajectory and possibly no blackout for the nominal trajectory. There is very little likelihood of a communications outage using X-band (however, X-band is not currently planned to be used during peak electron density phase of EDL).

Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling.

PubMed

Boone, Eric J; Laskin, Alexander; Laskin, Julia; Wirth, Christopher; Shepson, Paul B; Stirm, Brian H; Pratt, Kerri A

2015-07-21

Cloudwater and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry (HRMS) with nanospray desorption electrospray ionization (nano-DESI) and direct infusion electrospray ionization (ESI) were utilized to compare the organic composition of the particle and cloudwater samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloudwater, showing the significant influence of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloudwater samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloudwater when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.

Online Chapmann Layer Calculator for Simulating the Ionosphere with Undergraduate and Graduate Students

NASA Astrophysics Data System (ADS)

Gross, N. A.; Withers, P.; Sojka, J. J.

2014-12-01

The Chapman Layer Model is a "textbook" model of the ionosphere (for example, "Theory of Planetary Atmospheres" by Chamberlain and Hunten, Academic Press (1978)). The model use fundamental assumptions about the neutral atmosphere, the flux of ionizing radiation, and the recombination rate to calculation the ionization rate, and ion/electron density for a single species atmosphere. We have developed a "Chapman Layer Calculator" application that is deployed on the web using Java. It allows the user to see how various parameters control ion density, peak height, and profile of the ionospheric layer. Users can adjust parameters relevant to thermosphere scale height (temperature, gravitational acceleration, molecular weight, neutral atmosphere density) and to Extreme Ultraviolet solar flux (reference EUV, distance from the Sun, and solar Zenith Angle) and then see how the layer changes. This allows the user to simulate the ionosphere on other planets, by adjusting to the appropriate parameters. This simulation has been used as an exploratory activity for the NASA/LWS - Heliophysics Summer School 2014 and has an accompanying activity guide.

Aqueous Processing of Atmospheric Organic Particles in Cloud Water Collected via Aircraft Sampling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Boone, Eric J.; Laskin, Alexander; Laskin, Julia

2015-07-21

Cloud water and below-cloud atmospheric particle samples were collected onboard a research aircraft during the Southern Oxidant and Aerosol Study (SOAS) over a forested region of Alabama in June 2013. The organic molecular composition of the samples was studied to gain insights into the aqueous-phase processing of organic compounds within cloud droplets. High resolution mass spectrometry with nanospray desorption electrospray ionization and direct infusion electrospray ionization were utilized to compare the organic composition of the particle and cloud water samples, respectively. Isoprene and monoterpene-derived organosulfates and oligomers were identified in both the particles and cloud water, showing the significant influencemore » of biogenic volatile organic compound oxidation above the forested region. While the average O:C ratios of the organic compounds were similar between the atmospheric particle and cloud water samples, the chemical composition of these samples was quite different. Specifically, hydrolysis of organosulfates and formation of nitrogen-containing compounds were observed for the cloud water when compared to the atmospheric particle samples, demonstrating that cloud processing changes the composition of organic aerosol.« less

Atmospheric consequences of cosmic ray variability in the extragalactic shock model: 2. Revised ionization levels and their consequences

NASA Astrophysics Data System (ADS)

Melott, Adrian L.; Atri, Dimitra; Thomas, Brian C.; Medvedev, Mikhail V.; Wilson, Graham W.; Murray, Michael J.

2010-08-01

It has been suggested that galactic shock asymmetry induced by our galaxy's infall toward the Virgo Cluster may be a source of periodicity in cosmic ray exposure as the solar system oscillates perpendicular to the galactic plane, thereby, inducing an observed terrestrial periodicity in biodiversity. There are a number of plausible mechanisms by which cosmic rays might affect terrestrial biodiversity. Here we investigate one of these mechanisms, the consequent ionization and dissociation in the atmosphere, resulting in changes in atmospheric chemistry that culminate in the depletion of ozone and a resulting increase in the dangerous solar UVB flux on the ground. We use a heuristic model of the cosmic ray intensity enhancement originally suggested by Medvedev and Melott (2007) to compute steady state atmospheric effects. This paper is a reexamination of an issue we have studied before with a simplified approximation for the distribution of incidence angles. The new results are based on an improved ionization background computation averaged over a massive ensemble (about 7 × 105) shower simulations at various energies and incidence angles. We adopt a range with a minimal model and a fit to full exposure to the postulated extragalactic background. The atmospheric effects are greater than they were with our earlier, simplified ionization model. At the lower end of the intensity range, we find that the effects are too small to be of serious consequence. At the upper end of this range, ˜6% global average loss of ozone column density exceeds that currently experienced due to anthropogenic effects such as accumulated chlorofluorocarbons. We discuss some of the possible effects. The intensity of the atmospheric effects is less than those of a nearby supernova or galactic γ ray burst, but the duration of the effects would be about 106 times longer. Present UVB enhancement from current ozone depletion ˜3% is a documented stress on the biosphere, but a depletion of the magnitude found at the upper end of our range would approximately double the global average UVB flux. We conclude that for estimates at the upper end of the reasonable range of the cosmic ray variability over geologic time, the mechanism of atmospheric ozone depletion may provide a major biological stress, which could easily bring about major loss of biodiversity. It is possible that future high-energy astrophysical observations will resolve the question of whether such depletion is likely.

On the Magnetic Protection of the Atmosphere of Proxima Centauri b

NASA Astrophysics Data System (ADS)

Garcia-Sage, K.; Glocer, A.; Drake, J. J.; Gronoff, G.; Cohen, O.

2017-07-01

The discovery of exoplanets orbiting red dwarfs, such as Proxima Centauri b, has led to questions of their habitability and capacity to retain liquid surface water. While Proxima b is in a “temperate orbit,” I.e., an Earth at that location would not freeze or boil its oceans, its proximity to a parent star with quite high magnetic activity is likely to influence its atmospheric evolution and habitability. Planetary magnetic fields can prevent direct stripping away of the planetary atmosphere by the stellar wind, but ion escape can still occur at the magnetic poles. This process, the polar wind, is well known to occur at Earth and may have contributed to the habitability of Earth’s early atmosphere. The polar wind is highly variable and sensitive to both ionizing radiation and geomagnetic activity. The higher ionizing radiation levels of M dwarfs at habitable zone distances are expected to increase the polar wind by orders of magnitude and, instead of helping create a habitable atmosphere, may strip away enough volatiles to render the planet inhospitable. Here, we compute the ionospheric outflow of an Earth-twin subject to the enhanced stellar EUV flux of Proxima b, and the effect on atmospheric escape timescales. We show that an Earth-like planet would not survive the escape of its atmosphere at that location, and therefore the pathway to habitability for Proxima b requires a very different atmospheric history than that of Earth.

On the Magnetic Protection of the Atmosphere of Proxima Centauri b

DOE Office of Scientific and Technical Information (OSTI.GOV)

Garcia-Sage, K.; Glocer, A.; Drake, J. J.

The discovery of exoplanets orbiting red dwarfs, such as Proxima Centauri b, has led to questions of their habitability and capacity to retain liquid surface water. While Proxima b is in a “temperate orbit,” i.e., an Earth at that location would not freeze or boil its oceans, its proximity to a parent star with quite high magnetic activity is likely to influence its atmospheric evolution and habitability. Planetary magnetic fields can prevent direct stripping away of the planetary atmosphere by the stellar wind, but ion escape can still occur at the magnetic poles. This process, the polar wind, is wellmore » known to occur at Earth and may have contributed to the habitability of Earth’s early atmosphere. The polar wind is highly variable and sensitive to both ionizing radiation and geomagnetic activity. The higher ionizing radiation levels of M dwarfs at habitable zone distances are expected to increase the polar wind by orders of magnitude and, instead of helping create a habitable atmosphere, may strip away enough volatiles to render the planet inhospitable. Here, we compute the ionospheric outflow of an Earth-twin subject to the enhanced stellar EUV flux of Proxima b, and the effect on atmospheric escape timescales. We show that an Earth-like planet would not survive the escape of its atmosphere at that location, and therefore the pathway to habitability for Proxima b requires a very different atmospheric history than that of Earth.« less

A Versatile Integrated Ambient Ionization Source Platform.

PubMed

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-30

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. Graphical abstract ᅟ.

Forensic applications of ambient ionization mass spectrometry.

PubMed

Ifa, Demian R; Jackson, Ayanna U; Paglia, Giuseppe; Cooks, R Graham

2009-08-01

This review highlights and critically assesses forensic applications in the developing field of ambient ionization mass spectrometry. Ambient ionization methods permit the ionization of samples outside the mass spectrometer in the ordinary atmosphere, with minimal sample preparation. Several ambient ionization methods have been created since 2004 and they utilize different mechanisms to create ions for mass-spectrometric analysis. Forensic applications of these techniques--to the analysis of toxic industrial compounds, chemical warfare agents, illicit drugs and formulations, explosives, foodstuff, inks, fingerprints, and skin--are reviewed. The minimal sample pretreatment needed is illustrated with examples of analysis from complex matrices (e.g., food) on various substrates (e.g., paper). The low limits of detection achieved by most of the ambient ionization methods for compounds of forensic interest readily offer qualitative confirmation of chemical identity; in some cases quantitative data are also available. The forensic applications of ambient ionization methods are a growing research field and there are still many types of applications which remain to be explored, particularly those involving on-site analysis. Aspects of ambient ionization currently undergoing rapid development include molecular imaging and increased detection specificity through simultaneous chemical reaction and ionization by addition of appropriate chemical reagents.

A Versatile Integrated Ambient Ionization Source Platform

NASA Astrophysics Data System (ADS)

Ai, Wanpeng; Nie, Honggang; Song, Shiyao; Liu, Xiaoyun; Bai, Yu; Liu, Huwei

2018-04-01

The pursuit of high-throughput sample analysis from complex matrix demands development of multiple ionization techniques with complementary specialties. A versatile integrated ambient ionization source (iAmIS) platform is proposed in this work, based on the idea of integrating multiple functions, enhancing the efficiency of current ionization techniques, extending the applications, and decreasing the cost of the instrument. The design of the iAmIS platform combines flowing atmospheric pressure afterglow (FAPA) source/direct analysis in real time (DART), dielectric barrier discharge ionization (DBDI)/low-temperature plasma (LTP), desorption electrospray ionization (DESI), and laser desorption (LD) technique. All individual and combined ionization modes can be easily attained by modulating parameters. In particular, the FAPA/DART&DESI mode can realize the detection of polar and nonpolar compounds at the same time with two different ionization mechanisms: proton transfer and charge transfer. The introduction of LD contributes to the mass spectrometry imaging and the surface-assisted laser desorption (SALDI) under ambient condition. Compared with other individual or multi-mode ion source, the iAmIS platform provides the flexibility of choosing different ionization modes, broadens the scope of the analyte detection, and facilitates the analysis of complex samples. [Figure not available: see fulltext.

Modification of planetary atmospheres by material from the rings

NASA Technical Reports Server (NTRS)

Atreya, S. K.

1984-01-01

The modification of the atmospheres and ionospheres of ringed planets by the injection of ionized and neutral material from the rings is discussed, on the basis of Pioneer and Voyager observations. It is shown that although no direct evidence exists for the injection of material from the rings into the atmosphere, such an interaction could account for the observed thermal structure and ionospheric properties of Jupiter, Saturn, Uranus, and the Jovian satellite Io.

The precipitation of energetic heavy ions into the upper atmosphere of Jupiter

NASA Technical Reports Server (NTRS)

Horanyi, M.; Cravens, T. E.; Waite, J. H., Jr.

1987-01-01

Evidence for auroral particle precipitation at Jupiter was provided by the ultraviolet spectrometers onboard the Voyagers 1 and 2 spacecraft and by the International Ultraviolet Explorer (IUE). Magnetospheric measurements made by instruments onboard the Voyager spacecraft show that energetic sulfur and oxygen ions are precipitating into the upper atmosphere of Jupiter. A theoretical model has been constructed describing the interaction of precipitating oxygen with the Jovian atmosphere. The auroral energy is deposited in the atmosphere by means of ionization, excitation, and dissociation and heating of the atmospheric gas. Energetic ion and electron precipitation are shown to have similar effects on the atmosphere and ionosphere of Jupiter.

Modeling Planetary Atmospheric Energy Deposition By Energetic Ions

NASA Astrophysics Data System (ADS)

Parkinson, Christopher; Bougher, Stephen; Gronoff, Guillaume; Barthelemy, Mathieu

2016-07-01

The structure, dynamics, chemistry, and evolution of planetary upper atmospheres are in large part determined by the available sources of energy. In addition to the solar EUV flux, the solar wind and solar energetic particle (SEP) events are also important sources. Both of these particle populations can significantly affect an atmosphere, causing atmospheric loss and driving chemical reactions. Attention has been paid to these sources from the standpoint of the radiation environment for humans and electronics, but little work has been done to evaluate their impact on planetary atmospheres. At unmagnetized planets or those with crustal field anomalies, in particular, the solar wind and SEPs of all energies have direct access to the atmosphere and so provide a more substantial energy source than at planets having protective global magnetic fields. Additionally, solar wind and energetic particle fluxes should be more significant for planets orbiting more active stars, such as is the case in the early history of the solar system for paleo-Venus and Mars. Therefore quantification of the atmospheric energy input from the solar wind and SEP events is an important component of our understanding of the processes that control their state and evolution. We have applied a full Lorentz motion particle transport model to study the effects of particle precipitation in the upper atmospheres of Mars and Venus. Such modeling has been previously done for Earth and Mars using a guiding center precipitation model. Currently, this code is only valid for particles with small gyroradii in strong uniform magnetic fields. There is a clear necessity for a Lorentz formulation, hence, a systematic study of the ionization, excitation, and energy deposition has been conducted, including a comparison of the influence relative to other energy sources (namely EUV photons). The result is a robust examination of the influence of energetic ion transport on the Venus and Mars upper atmosphere which will be discussed in this presentation.

Thermal diffusion in partially ionized gases - The case of unequal temperatures. [in solar chromosphere

NASA Technical Reports Server (NTRS)

Geiss, J.; Burgi, A.

1987-01-01

Previous calculations of thermal diffusion coefficients in partially ionized gases are extended to the case of unequal neutral and ion temperatures and/or temperature gradients. Formulas are derived for the general case of a major gas as well as for minor atoms and ions. Strong enhancements of minor-ion thermal diffusion coefficients over their values in the fully ionized gas are found when the degree of ionization in the main gas is relatively low. However, compared to the case of equal temperatures, the enhancements are less strong when the neutrals are cooler than the ions. The specific case of the H-H(+) mixture, which is important in the study of solar and stellar atmospheres, is discussed as an application.

Comparative study of fourteen alkaloids from Uncaria rhynchophylla hooks and leaves using HPLC-diode array detection-atmospheric pressure chemical ionization/MS method.

PubMed

Qu, Jialin; Gong, Tianxing; Ma, Bin; Zhang, Lin; Kano, Yoshihiro; Yuan, Dan

2012-01-01

The purpose of the study is to compare alkaloid profile of Uncaria rhynchophylla hooks and leaves. Ten oxindole alkaloids and four glycosidic indole alkaloids were identified using HPLC-diode array detection (DAD) or LC-atmospheric pressure chemical ionization (APCI)-MS method, and a HPLC-UV method for simultaneous quantification of major alkaloids was validated. The hooks are characterized by high levels of four oxindole alkaloids rhynchophylline (R), isorhynchophylline (IR), corynoxeine (C) and isocorynoxeine (IC), while the leaves contained high level of two glycosidic indole alkaloids vincoside lactam (VL) and strictosidine (S). The presented methods have proven its usefulness in chemical characterization of U. rhynchophylla hooks and leaves.

Collision effects on propagation characteristics of electromagnetic waves in a sub-wavelength plasma slab of partially ionized dense plasmas

NASA Astrophysics Data System (ADS)

Bowen, LI; Zhibin, WANG; Qiuyue, NIE; Xiaogang, WANG; Fanrong, KONG; Zhenyu, WANG

2018-01-01

Intensive collisions between electrons and neutral particles in partially ionized plasmas generated in atmospheric/sub-atmospheric pressure environments can sufficiently affect the propagation characteristics of electromagnetic waves, particularly in the sub-wavelength regime. To investigate the collisional effect in such plasmas, we introduce a simplified plasma slab model with a thickness on the order of the wavelength of the incident electromagnetic wave. The scattering matrix method (SMM) is applied to solve the wave equation in the plasma slab with significant nonuniformity. Results show that the collisions between the electrons and the neutral particles, as well as the incident angle and the plasma thickness, can disturb the transmission and reduce reflection significantly.

Comparison of Air Fluorescence and Ionization Measurements of E.M. Shower Depth Profiles: Test of a UHECR Detector Technique

DOE Office of Scientific and Technical Information (OSTI.GOV)

Belz, J.; Cao, Z.; Huentemeyer, P.

Measurements are reported on the fluorescence of air as a function of depth in electromagnetic showers initiated by bunches of 28.5 GeV electrons. The light yield is compared with the expected and observed depth profiles of ionization in the showers. It validates the use of atmospheric fluorescence profiles in measuring ultra high energy cosmic rays.

A corona discharge atmospheric pressure chemical ionization source with selective NO(+) formation and its application for monoaromatic VOC detection.

PubMed

Sabo, Martin; Matejčík, Štefan

2013-11-21

We have developed a new type of corona discharge (CD) for atmospheric pressure chemical ionization (APCI) for application in ion mobility spectrometry (IMS) as well as in mass spectrometry (MS). While the other CD-APCI sources are able to generate H3O(+)·(H2O)n as the major reactant ions in N2 or in zero air, the present CD-APCI source has the ability to generate up to 84% NO(+)·(H2O)n reactant ions in zero air. The change of the working gas from zero air to N2 allows us to change the major reactant ions from NO(+)·(H2O)n to H3O(+)·(H2O)n. In this paper we present the description of the new CD-APCI and discuss the processes associated with the NO(+) formation. The selective formation of NO(+)·(H2O)n reactant ions offers chemical ionization based on these ions which can be of great advantage for some classes of chemicals. We demonstrate here a significant increase in the sensitivity of the IMS-MS instrument for monoaromatic volatile organic compound (VOC) detection upon NO(+)·(H2O)n chemical ionization.

Development of a Sodium Resonance Lidar for Spaceborne Missions

NASA Astrophysics Data System (ADS)

Janches, D.; Krainak, M. A.; Yu, A. W.; Oleg, K. A.; Jones, S.; Huang, R.

2016-12-01

Layers of neutral metal atoms (i.e. Fe, Mg, Ca, K, Na), which peak between 85 and 95 km and are 20 km in width, are produced by the daily ablation of billions of Interplanetary Dust Particles (IDPs). As these metallic species are ionized during ablation, by sunlights ultraviolet photons, or by charge exchange with existing atmospheric ions, meteoroids affect the structure, chemistry, dynamics, and energetics of the Mesosphere and Lower Thermosphere (MLT). In particular, the strong optical signals produced by the Na layer, makes it an optimal tracer of atmospheric dynamics and circulation and enabling the measurement of quantities, such as composition, temperature and winds, that are critical to address several compelling scientific questions related to the Earth's Upper Atmosphere and the Geospace Environment. In particular, there is a pressing need in the Ionosphere-Thermosphere-Mesosphere (ITM) community to be able to perform high resolution measurements that can be used to characterize the small-scale variability in the MLT on a global basis. Such measurements must include highly resolved, in space and time, global temperatures profiles, which will add to the understanding of key indicators of radiative cooling in the mesosphere. We present in this paper a status update of the efforts carried out at NASA/GSFC to develop and demonstrate an integrated ground-based operational sodium lidar science instrument. The instrument, which uses key space-flight-precursor components, has currently a Technology Readiness Level (TRL) 4. Efforts to raise its TRL to 6 will be presented to demonstrate the spaceflight instrument viability in a cost-efficient approach and serve as the core for the future planning of a Heliophysics space mission.

Remote sensing applications for diagnostics of the radioactive pollution of the ground surface and in the atmosphere

NASA Astrophysics Data System (ADS)

Pulinets, Sergey; Ouzounov, Dimitar; Boyarchuk, Kirill; Laverov, Nikolay

2013-04-01

Radioactive pollution due to its air ionization activity can drastically change the atmospheric boundary layer conductivity (what was experimentally proved during period of nuclear tests in atmosphere) and through the global electric circuit produce anomalous variations in atmosphere. As additional effect the ions created due to air ionization serve as centers of water vapor condensation and nucleation of aerosol-size particles. This process is accompanied by latent heat release. Both anomalies (ionospheric and thermal) can be controlled by remote sensing technique both from satellites (IR sensors and ionospheric probes) and from ground (GPS receivers, ground based ionosondes, VLF propagation sounding, ground measurements of the air temperature and humidity). We monitored the majority of transient events (Three-Mile Island and Chernobyl nuclear power plant emergencies) and stationary sources such as Gabon natural nuclear reactor, sites of underground nuclear tests, etc. and were able to detect thermal anomalies and for majority of cases - the ionospheric anomalies as well. Immediately after the March 11, 2011 earthquake and tsunami in Japan we started to continuously survey the long-wavelength energy flux (10-13 microns) measurable at top of the atmosphere from POES/NOAA/AVHRR polar orbit satellites. Our preliminary results show the presence of hot spots on the top of the atmosphere over the Fukushima Daiichi Nuclear Power Plant (FDNPP) and due to their persistence over the same region they are most likely not of meteorological origin. On March 14 and 21 we detected a significant increase in radiation at the top of the atmosphere which also coincides with a reported radioactivity gas leaks from the FDNPP. After March 21 the intensity of energy flux in atmosphere started to decline, which has been confirmed by ground radiometer network. We were able to detect with ground based ionosonde the ionospheric anomaly associated with the largest radioactive release on March 21.We are presenting new theoretical estimates and results of experimental measurements showing that the heat flux released during ionization of the atmospheric boundary layer under significant radioactive pollution is sufficient for recording anomalous heat fluxes using the means of remote sounding (infrared radiometers) installed on satellites, and ionospheric anomalies are generated due to changes of the boundary layer conductivity.

Dynamics of bulk electron heating and ionization in solid density plasmas driven by ultra-short relativistic laser pulses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Huang, L. G., E-mail: lingen.huang@hzdr.de; Kluge, T.; Cowan, T. E.

The dynamics of bulk heating and ionization is investigated both in simulations and theory, which determines the crucial plasma parameters such as plasma temperature and density in ultra-short relativistic laser-solid target interactions. During laser-plasma interactions, the solid density plasma absorbs a fraction of laser energy and converts it into kinetic energy of electrons. A portion of the electrons with relativistic kinetic energy goes through the solid density plasma and transfers energy into the bulk electrons, which results in bulk electron heating. The bulk electron heating is finally translated into the processes of bulk collisional ionization inside the solid target. Amore » simple model based on the Ohmic heating mechanism indicates that the local and temporal profile of bulk return current is essential to determine the temporal evolution of bulk electron temperature. A series of particle-in-cell simulations showing the local heating model is robust in the cases of target with a preplasma and without a preplasma. Predicting the bulk electron heating is then benefit for understanding the collisional ionization dynamics inside the solid targets. The connection of the heating and ionization inside the solid target is further studied using Thomas-Fermi model.« less

Importance of biologically active aurora-like ultraviolet emission: stochastic irradiation of Earth and Mars by flares and explosions.

PubMed

Smith, David S; Scalo, John; Wheeler, J Craig

2004-10-01

Habitable planets will be subject to intense sources of ionizing radiation and fast particles from a variety of sources--from the host star to distant explosions--on a variety of timescales. Monte Carlo calculations of high-energy irradiation suggest that the surfaces of terrestrial-like planets with thick atmospheres (column densities greater than about 100 g cm(-2)) are well protected from directly incident X-rays and gamma-rays, but we find that sizeable fractions of incident ionizing radiation from astrophysical sources can be redistributed to biologically and chemically important ultraviolet wavelengths, a significant fraction of which can reach the surface. This redistribution is mediated by secondary electrons, resulting from Compton scattering and X-ray photoabsorption, the energies of which are low enough to excite and ionize atmospheric molecules and atoms, resulting in a rich aurora-like spectrum. We calculate the fraction of energy redistributed into biologically and chemically important wavelength regions for spectra characteristic of stellar flares and supernovae using a Monte-Carlo transport code and then estimate the fraction of this energy that is transmitted from the atmospheric altitudes of redistribution to the surface for a few illustrative cases. For atmospheric models corresponding to the Archean Earth, we assume no significant ultraviolet absorbers, only Rayleigh scattering, and find that the fraction of incident ionizing radiation that is received at the surface in the form of redistributed ultraviolet in the biologically relevant 200-320 nm region (UV-C and UV-B bands) can be up to 4%. On the present-day Earth with its ultraviolet ozone shield, this fraction is found to be 0.2%. Both values are many orders of magnitude higher than the fraction of direct ionizing radiation reaching the surface. This result implies that planetary organisms will be subject to mutationally significant, if intermittent, fluences of UV-B and harder radiation even in the presence of a narrow-band ultraviolet shield like ozone. We also calculate the surficial transmitted fraction of ionizing radiation and redistributed ultraviolet radiation for two illustrative evolving Mars atmospheres whose initial surface pressures were 1 bar. We discuss the frequency with which redistributed ultraviolet flux from parent star flares exceeds the parent star ultraviolet flux at the planetary surface. We find that the redistributed ultraviolet from parent star flares is probably a fairly rare intermittent event for habitable zone planets orbiting solar-type stars except when they are young, but should completely dominate the direct steady ultraviolet radiation from the parent star for planets orbiting all stars less massive than about 0.5 solar masses. Our results suggest that coding organisms on such planets (and on the early Earth) may evolve very differently than on contemporary Earth, with diversity and evolutionary rate controlled by a stochastically varying mutation rate and frequent hypermutation episodes.

The determination of carbon dioxide concentration using atmospheric pressure ionization mass spectrometry/isotopic dilution and errors in concentration measurements caused by dryers.

PubMed

DeLacy, Brendan G; Bandy, Alan R

2008-01-01

An atmospheric pressure ionization mass spectrometry/isotopically labeled standard (APIMS/ILS) method has been developed for the determination of carbon dioxide (CO(2)) concentration. Descriptions of the instrumental components, the ionization chemistry, and the statistics associated with the analytical method are provided. This method represents an alternative to the nondispersive infrared (NDIR) technique, which is currently used in the atmospheric community to determine atmospheric CO(2) concentrations. The APIMS/ILS and NDIR methods exhibit a decreased sensitivity for CO(2) in the presence of water vapor. Therefore, dryers such as a nafion dryer are used to remove water before detection. The APIMS/ILS method measures mixing ratios and demonstrates linearity and range in the presence or absence of a dryer. The NDIR technique, on the other hand, measures molar concentrations. The second half of this paper describes errors in molar concentration measurements that are caused by drying. An equation describing the errors was derived from the ideal gas law, the conservation of mass, and Dalton's Law. The purpose of this derivation was to quantify errors in the NDIR technique that are caused by drying. Laboratory experiments were conducted to verify the errors created solely by the dryer in CO(2) concentration measurements post-dryer. The laboratory experiments verified the theoretically predicted errors in the derived equations. There are numerous references in the literature that describe the use of a dryer in conjunction with the NDIR technique. However, these references do not address the errors that are caused by drying.

Liquid chromatography coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry and post-column addition of metal salt solutions as a powerful tool for the metabolic profiling of Fusarium oxysporum.

PubMed

Cirigliano, Adriana M; Rodriguez, M Alejandra; Gagliano, M Laura; Bertinetti, Brenda V; Godeas, Alicia M; Cabrera, Gabriela M

2016-03-25

Fusarium oxysporum L11 is a non-pathogenic soil-borne fungal strain that yielded an extract that showed antifungal activity against phytopathogens. In this study, reversed-phase high-performance liquid chromatography (RP-HPLC) coupled to different atmospheric pressure ionization sources-quadrupole-time-of-flight mass spectrometry (API-QTOF-MS) was applied for the comprehensive profiling of the metabolites from the extract. The employed sources were electrospray (ESI), atmospheric pressure chemical ionization (APCI) and atmospheric pressure photoionization (APPI). Post-column addition of metal solutions of Ca, Cu and Zn(II) was also tested using ESI. A total of 137 compounds were identified or tentatively identified by matching their accurate mass signals, suggested molecular formulae and MS/MS analysis with previously reported data. Some compounds were isolated and identified by NMR. The extract was rich in cyclic peptides like cyclosporins, diketopiperazines and sansalvamides, most of which were new, and are reported here for the first time. The use of post-column addition of metals resulted in a useful strategy for the discrimination of compound classes since specific adducts were observed for the different compound families. This technique also allowed the screening for compounds with metal binding properties. Thus, the applied methodology is a useful choice for the metabolic profiling of extracts and also for the selection of metabolites with potential biological activities related to interactions with metal ions. Copyright © 2015 Elsevier B.V. All rights reserved.

A Dynamic/Anisotropic Low Earth Orbit (LEO) Ionizing Radiation Model

NASA Technical Reports Server (NTRS)

Badavi, Francis F.; West, Katie J.; Nealy, John E.; Wilson, John W.; Abrahms, Briana L.; Luetke, Nathan J.

2006-01-01

The International Space Station (ISS) provides the proving ground for future long duration human activities in space. Ionizing radiation measurements in ISS form the ideal tool for the experimental validation of ionizing radiation environmental models, nuclear transport code algorithms, and nuclear reaction cross sections. Indeed, prior measurements on the Space Transportation System (STS; Shuttle) have provided vital information impacting both the environmental models and the nuclear transport code development by requiring dynamic models of the Low Earth Orbit (LEO) environment. Previous studies using Computer Aided Design (CAD) models of the evolving ISS configurations with Thermo Luminescent Detector (TLD) area monitors, demonstrated that computational dosimetry requires environmental models with accurate non-isotropic as well as dynamic behavior, detailed information on rack loading, and an accurate 6 degree of freedom (DOF) description of ISS trajectory and orientation.

Dynamics of light-field control of molecular dissociation at the few-cycle limit.

PubMed

Tong, X M; Lin, C D

2007-03-23

We studied the laser-molecule interaction dynamics that leads to the asymmetric D+ ion ejection in the dissociative ionization of D2 molecules observed recently in Kling et al. [Science 312, 246 (2006)10.1126/science.1126259]. By changing the carrier-envelope phase, we showed that the asymmetry is a consequence of manipulating the initial ionization and the rescattering of the electrons within one optical cycle of the laser. The result illustrates the feasibility of coherent control of reaction dynamics at the attosecond time scale.

Effect of a finite ionization rate on the radiative heating of outer planet atmospheric entry probes

NASA Technical Reports Server (NTRS)

Nelson, H. F.

1981-01-01

The influence of finite rate ionization in the inviscid gas just behind the stagnation shock wave on the radiation heating of probes entering the hydrogen helium atmospere of the major planets was investigated. At the present time, there is disagreement as to whether the radiative flux increases or decreases relative to its equilibrium value when finite rate ionization is considered. Leibowitz and Kuo content that the finite rate ionization in the hydrogen gas just behind the shock wave reduces the radiative flux to the probe, whereas Tiwari and Szema predict that it increases the radiative flux. The radiation modeling used in the calculations of both pairs of these investigators was reviewed. It is concluded that finite rate ionization in the inviscid region of the shock layer should reduce the cold wall radiative heating below the values predicted by equilibrium chemistry assumptions.

Absolute measurement of the extreme UV solar flux

NASA Technical Reports Server (NTRS)

Carlson, R. W.; Ogawa, H. S.; Judge, D. L.; Phillips, E.

1984-01-01

A windowless rare-gas ionization chamber has been developed to measure the absolute value of the solar extreme UV flux in the 50-575-A region. Successful results were obtained on a solar-pointing sounding rocket. The ionization chamber, operated in total absorption, is an inherently stable absolute detector of ionizing UV radiation and was designed to be independent of effects from secondary ionization and gas effusion. The net error of the measurement is + or - 7.3 percent, which is primarily due to residual outgassing in the instrument, other errors such as multiple ionization, photoelectron collection, and extrapolation to the zero atmospheric optical depth being small in comparison. For the day of the flight, Aug. 10, 1982, the solar irradiance (50-575 A), normalized to unit solar distance, was found to be 5.71 + or - 0.42 x 10 to the 10th photons per sq cm sec.

Ionization dynamics of the water trimer: A direct ab initio MD study

NASA Astrophysics Data System (ADS)

Tachikawa, Hiroto; Takada, Tomoya

2013-03-01

Ionization dynamics of the cyclic water trimer (H2O)3 have been investigated by means of direct ab initio molecular dynamics (AIMD) method. Two reaction channels, complex formation and OH dissociation, were found following the ionization of (H2O)3. In both channels, first, a proton was rapidly transferred from H2O+ to H2O (time scale is ˜15 fs after the ionization). In complex channel, an ion-radical contact pair (H3O+-OH) solvated by the third water molecule was formed as a long-lived H3O+(OH)H2O complex. In OH dissociation channel, the second proton transfer further takes place from H3O+(OH) to H2O (time scale is 50-100 fs) and the OH radical is separated from the H3O+. At the same time, the OH dissociation takes place when the excess energy is efficiently transferred into the kinetic energy of OH radical. The OH dissociation channel is significantly minor, and almost all product channels were the complex formation. The reaction mechanism was discussed on the basis of theoretical results.

Particle in cell simulation on plasma grating contrast enhancement induced by infrared laser pulse

NASA Astrophysics Data System (ADS)

Li, M.; Yuan, T.; Xu, Y. X.; Wang, J. X.; Luo, S. N.

2018-05-01

The dynamics of plasma grating contrast enhancement (PGCE) irradiated by an infrared laser pulse is investigated with one dimensional particle-in-cell simulation where field ionization and impact ionization are simultaneously considered for the first time. The numeric results show that the impact ionization dominates the PGCE process. Upon the interaction with the laser pulse, abundant free electrons are efficiently accelerated and subsequently triggered massive impact ionizations in the density ridges of the plasma grating for the higher local plasma energy density, which efficiently enhances the grating contrast. Besides the dynamic analysis of PGCE, we explore the parameter space of the incident infrared laser pulse to optimize the PGCE effect, which can provide useful guidance to experiments related to laser-plasma-grating interactions and may find applications in prolonging the duration of the plasma grating.

Ultrasensitive Ambient Mass Spectrometric Analysis with a Pin-to-Capillary Flowing Atmospheric-Pressure Afterglow Source

PubMed Central

Shelley, Jacob T.; Wiley, Joshua S.; Hieftje, Gary M.

2011-01-01

The advent of ambient desorption/ionization mass spectrometry has resulted in a strong interest in ionization sources that are capable of direct analyte sampling and ionization. One source that has enjoyed increasing interest is the Flowing Atmospheric-Pressure Afterglow (FAPA). FAPA has been proven capable of directly desorbing/ionizing samples in any phase (solid, liquid, or gas) and with impressive limits of detection (<100 fmol). The FAPA was also shown to be less affected by competitive-ionization matrix effects than other plasma-based sources. However, the original FAPA design exhibited substantial background levels, cluttered background spectra in the negative-ion mode, and significant oxidation of aromatic analytes, which ultimately compromised analyte identification and quantification. In the present study, a change in the FAPA configuration from a pin-to-plate to a pin-to-capillary geometry was found to vastly improve performance. Background signals in positive- and negative-ionization modes were reduced by 89% and 99%, respectively. Additionally, the capillary anode strongly reduced the amount of atomic oxygen that could cause oxidation of analytes. Temperatures of the gas stream that interacts with the sample, which heavily influences desorption capabilities, were compared between the two sources by means of IR thermography. The performance of the new FAPA configuration is evaluated through the determination of a variety of compounds in positive- and negative-ion mode, including agrochemicals and explosives. A detection limit of 4 amol was found for the direct determination of the agrochemical ametryn, and appears to be spectrometer-limited. The ability to quickly screen for analytes in bulk liquid samples with the pin-to-capillary FAPA is also shown. PMID:21627097

Ultrasensitive ambient mass spectrometric analysis with a pin-to-capillary flowing atmospheric-pressure afterglow source.

PubMed

Shelley, Jacob T; Wiley, Joshua S; Hieftje, Gary M

2011-07-15

The advent of ambient desorption/ionization mass spectrometry has resulted in a strong interest in ionization sources that are capable of direct analyte sampling and ionization. One source that has enjoyed increasing interest is the flowing atmospheric-pressure afterglow (FAPA). The FAPA has been proven capable of directly desorbing/ionizing samples in any phase (solid, liquid, or gas) and with impressive limits of detection (<100 fmol). The FAPA was also shown to be less affected by competitive-ionization matrix effects than other plasma-based sources. However, the original FAPA design exhibited substantial background levels, cluttered background spectra in the negative-ion mode, and significant oxidation of aromatic analytes, which ultimately compromised analyte identification and quantification. In the present study, a change in the FAPA configuration from a pin-to-plate to a pin-to-capillary geometry was found to vastly improve performance. Background signals in positive- and negative-ionization modes were reduced by 89% and 99%, respectively. Additionally, the capillary anode strongly reduced the amount of atomic oxygen that could cause oxidation of analytes. Temperatures of the gas stream that interacts with the sample, which heavily influences desorption capabilities, were compared between the two sources by means of IR thermography. The performance of the new FAPA configuration is evaluated through the determination of a variety of compounds in positive- and negative-ion mode, including agrochemicals and explosives. A detection limit of 4 amol was found for the direct determination of the agrochemical ametryn and appears to be spectrometer-limited. The ability to quickly screen for analytes in bulk liquid samples with the pin-to-capillary FAPA is also shown.

Synthetic oligomer analysis using atmospheric pressure photoionization mass spectrometry at different photon energies.

PubMed

Desmazières, Bernard; Legros, Véronique; Giuliani, Alexandre; Buchmann, William

2014-01-15

Atmospheric pressure photoionization (APPI) followed by mass spectrometric detection was used to ionize a variety of polymers: polyethylene glycol, polymethyl methacrylate, polystyrene, and polysiloxane. In most cases, whatever the polymer or the solvent used (dichloromethane, tetrahydrofuran, hexane, acetone or toluene), only negative ion mode produced intact ions such as chlorinated adducts, with no or few fragmentations, in contrast to the positive ion mode that frequently led to important in-source fragmentations. In addition, it was shown that optimal detection of polymer distributions require a fine tuning of other source parameters such as temperature and ion transfer voltage. Series of mass spectra were recorded in the negative mode, in various solvents (dichloromethane, tetrahydrofuran, hexane, toluene, and acetone), by varying the photon energy from 8eV up to 10.6eV using synchrotron radiation. To these solvents, addition of a classical APPI dopant (toluene or acetone) was not necessary. Courtesy of the synchrotron radiation, it was demonstrated that the photon energy required for an efficient ionization of the polymer was correlated to the ionization energy of the solvent. As commercial APPI sources typically use krypton lamps with energy fixed at 10eV and 10.6eV, the study of the ionization of polymers over a wavelength range allowed to confirm and refine the previously proposed ionization mechanisms. Moreover, the APPI source can efficiently be used as an interface between size exclusion chromatography or reverse phase liquid chromatography and MS for the study of synthetic oligomers. However, the photoionization at fixed wavelength of polymer standards with different molecular weights showed that it was difficult to obtain intact ionized oligomers with molecular weights above a few thousands. Copyright © 2013 Elsevier B.V. All rights reserved.

Ionospheric Impacts on UHF Space Surveillance

NASA Astrophysics Data System (ADS)

Jones, J. C.

2017-12-01

Earth's atmosphere contains regions of ionized plasma caused by the interaction of highly energetic solar radiation. This region of ionization is called the ionosphere and varies significantly with altitude, latitude, local solar time, season, and solar cycle. Significant ionization begins at about 100 km (E layer) with a peak in the ionization at about 300 km (F2 layer). Above the F2 layer, the atmosphere is mostly ionized but the ion and electron densities are low due to the unavailability of neutral molecules for ionization so the density decreases exponentially with height to well over 1000 km. The gradients of these variations in the ionosphere play a significant role in radio wave propagation. These gradients induce variations in the index of refraction and cause some radio waves to refract. The amount of refraction depends on the magnitude and direction of the electron density gradient and the frequency of the radio wave. The refraction is significant at HF frequencies (3-30 MHz) with decreasing effects toward the UHF (300-3000 MHz) range. UHF is commonly used for tracking of space objects in low Earth orbit (LEO). While ionospheric refraction is small for UHF frequencies, it can cause errors in range, azimuth angle, and elevation angle estimation by ground-based radars tracking space objects. These errors can cause significant errors in precise orbit determinations. For radio waves transiting the ionosphere, it is important to understand and account for these effects. Using a sophisticated radio wave propagation tool suite and an empirical ionospheric model, we calculate the errors induced by the ionosphere in a simulation of a notional space surveillance radar tracking objects in LEO. These errors are analyzed to determine daily, monthly, annual, and solar cycle trends. Corrections to surveillance radar measurements can be adapted from our simulation capability.

Space Experiments with Particle Accelerators: SEPAC

NASA Technical Reports Server (NTRS)

Burch, J. L.; Roberts, W. T.; Taylor, W. W. L.; Kawashima, N.; Marshall, J. A.; Moses, S. L.; Neubert, T.; Mende, S. B.; Choueiri, E. Y.

1994-01-01

The Space Experiments with Particle Accelerators (SEPAC), which flew on the Atmospheric Laboratory for Applications and Science (ATLAS) 1 mission, used new techniques to study natural phenomena in the Earth's upper atmosphere, ionosphere and magnetosphere by introducing energetic perturbations into the system from a high power electron beam with known characteristics. Properties of auroras were studied by directing the electron beam into the upper atmosphere while making measurements of optical emissions. Studies were also performed of the critical ionization velocity phenomenon.

Radiation dose predictions for SPE events during solar cycle 23 from NASA's Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) model

NASA Astrophysics Data System (ADS)

Mertens, Christopher; Blattnig, Steve; Slaba, Tony; Kress, Brian; Wiltberger, Michael; Solomon, Stan

NASA's High Charge and Energy Transport (HZETRN) code is a deterministic model for rapid and accurate calculations of the particle radiation fields in the space environment. HZETRN is used to calculate dosimetric quantities on the International Space Station (ISS) and assess astronaut risk to space radiations, including realistic spacecraft and human geometry for final exposure evaluation. HZETRN is used as an engineering design tool for materials research for radiation shielding protection. Moreover, it is used to calculate HZE propagation through the Earth and Martian atmospheres, and to evaluate radiation exposures for epidemiological studies. A new research project has begun that will use HZETRN as the transport engine for the development of a nowcast prediction of air-crew radiation exposure for both background galactic cosmic ray (GCR) exposure and radiation exposure during solar particle events (SPE) that may accompany solar storms. The new air-crew radiation exposure model is called the Nowcast of Atmospheric Ionizing Radiation for Aviation Safety (NAIRAS) model, which utilizes real-time observations from ground-based, atmospheric, and satellite measurements. In this paper, we compute the global distribution of atmospheric radiation dose for several SPE events during solar cycle 23, with particular emphasis on the high-latitude and polar region. We also characterize the suppression of the geomagnetic cutoff rigidity during these storm periods and their subsequent influence on atmospheric radiation exposure.

The Response of High Energy Photoelectrons in The Mars Atmosphere to Variable Solar Input

NASA Astrophysics Data System (ADS)

Mills, I. F.; Eparvier, F. G.; Thiemann, E.; Mitchell, D. L.

2016-12-01

The Mars Atmosphere and Volatile Evolution (MAVEN) mission aims to understand the processes by which Mars has been losing atmosphere over time by analyzing data taken from different levels of the Martian atmosphere as well as solar drivers. In this project, we isolate data taken from the ionosphere to study high-energy electrons created by a particular ionization process called the Auger effect. This process occurs when soft x-rays ionize atmospheric gases. In particular, we focus on Auger electrons that are ionized from CO2 molecules and atomic O via solar irradiance in the 0.1-6 nm wavelength range. Thus far, the portion of the solar spectrum that produces Auger electrons has been sparsely measured and its spectral distribution is poorly understood, especially as a function of solar activity. To make up for this, models of spectral irradiance are used in studies of atmospheric effects. In an effort to validate solar irradiance models from 0.1- 6 nm, we utilize data from two instruments on board the MAVEN spacecraft, EUVM (the Extreme Ultraviolet Monitor), which measures the broadband solar irradiance from 0.1-6 nm and SWEA (the Solar Wind Electron Analyzer), which measures the photoelectron energy spectrum in the Mars atmosphere. We then compare these observed data sets to two different spectral irradiance models: MAVEN SynRef, and FISM-M (the Flare Irradiance Spectral Model for Mars). SynRef is a version of the SORCE XPS model modified to be used by MAVEN/EUVM, and FISM-M is a version of the FISM proxy model previously developed for Earth irradiance and modified to be used by MAVEN/EUVM. Our method of comparison is to find the Pearson correlation between the data and the models over October 2015, a month that had a strong solar rotational variability in the solar irradiance. By filtering the SWEA data for different altitudes and solar zenith angles, we are able to analyze how Auger electrons react under different solar activity levels. Both irradiance models correlate well with the electron data, specifically when comparing them with electrons in the bin containing the Auger peak, and when integrating over multiple energy bins surrounding this peak.

Weak-field few-femtosecond VUV photodissociation dynamics of water isotopologues

NASA Astrophysics Data System (ADS)

Baumann, Arne; Bazzi, Sophia; Rompotis, Dimitrios; Schepp, Oliver; Azima, Armin; Wieland, Marek; Popova-Gorelova, Daria; Vendrell, Oriol; Santra, Robin; Drescher, Markus

2017-07-01

We present a joint experimental and theoretical study of the VUV-induced dynamics of H2O and its deuterated isotopologues in the first excited state (A ˜1B1 ) utilizing a VUV-pump VUV-probe scheme combined with a b initio classical trajectory calculations. 16-fs VUV pulses centered at 161 nm created by fifth-order harmonic generation are employed for single-shot pump-probe measurements. Combined with a precise determination of the VUV pulses' temporal profile, they provide the necessary temporal resolution to elucidate sub-10-fs dissociation dynamics in the 1+1 photon ionization time window. Ionization with a single VUV photon complements established strong-field ionization schemes by disclosing the molecular dynamics under perturbative conditions. Kinetic isotope effects derived from the pump-probe experiment are found to be in agreement with our by ab initio classical trajectory calculations, taking into account photoionization cross sections for the ground and first excited state of the water cation.

Halo-shaped Flowing Atmospheric Pressure Afterglow – a Heavenly New Design for Simplified Sample Introduction and Improved Ionization in Ambient Mass Spectrometry

PubMed Central

Pfeuffer, Kevin P.; Schaper, J. Niklas; Shelley, Jacob T.; Ray, Steven J.; Chan, George C.-Y.; Bings, Nicolas H.; Hieftje, Gary M.

2013-01-01

The flowing atmospheric pressure afterglow (FAPA) is a promising new source for atmospheric pressure, ambient desorption/ionization mass spectrometry. However, problems exist with reproducible sample introduction into the FAPA source. To overcome this limitation, a new FAPA geometry has been developed in which concentric tubular electrodes are utilized to form a halo-shaped discharge; this geometry has been termed the halo-FAPA or h-FAPA. With this new geometry, it is still possible to achieve direct desorption and ionization from a surface; however, sample introduction through the inner capillary is also possible and improves interaction between the sample material (solution, vapor, or aerosol) and the plasma to promote desorption and ionization. The h-FAPA operates with a helium gas flow of 0.60 L/min outer, 0.30 L/min inner, applied current of 30 mA at 200 V for 6 watts of power. In addition, separation of the discharge proper and sample material prevents perturbations to the plasma. Optical-emission characterization and gas rotational temperatures reveal that the temperature of the discharge is not significantly affected (< 3% change at 450K) by water vapor during solution-aerosol sample introduction. The primary mass-spectral background species are protonated water clusters, and the primary analyte ions are protonated molecular ions (M+H+). Flexibility of the new ambient sampling source is demonstrated by coupling it with a laser ablation unit, a concentric nebulizer and a droplet-on-demand system for sample introduction. A novel arrangement is also presented in which the central channel of the h-FAPA is used as the inlet to a mass spectrometer. PMID:23808829

Halo-shaped flowing atmospheric pressure afterglow: a heavenly design for simplified sample introduction and improved ionization in ambient mass spectrometry.

PubMed

Pfeuffer, Kevin P; Schaper, J Niklas; Shelley, Jacob T; Ray, Steven J; Chan, George C-Y; Bings, Nicolas H; Hieftje, Gary M

2013-08-06

The flowing atmospheric-pressure afterglow (FAPA) is a promising new source for atmospheric-pressure, ambient desorption/ionization mass spectrometry. However, problems exist with reproducible sample introduction into the FAPA source. To overcome this limitation, a new FAPA geometry has been developed in which concentric tubular electrodes are utilized to form a halo-shaped discharge; this geometry has been termed the halo-FAPA or h-FAPA. With this new geometry, it is still possible to achieve direct desorption and ionization from a surface; however, sample introduction through the inner capillary is also possible and improves interaction between the sample material (solution, vapor, or aerosol) and the plasma to promote desorption and ionization. The h-FAPA operates with a helium gas flow of 0.60 L/min outer, 0.30 L/min inner, and applied current of 30 mA at 200 V for 6 W of power. In addition, separation of the discharge proper and sample material prevents perturbations to the plasma. Optical-emission characterization and gas rotational temperatures reveal that the temperature of the discharge is not significantly affected (<3% change at 450 K) by water vapor during solution-aerosol sample introduction. The primary mass-spectral background species are protonated water clusters, and the primary analyte ions are protonated molecular ions (M + H(+)). Flexibility of the new ambient sampling source is demonstrated by coupling it with a laser ablation unit, a concentric nebulizer, and a droplet-on-demand system for sample introduction. A novel arrangement is also presented in which the central channel of the h-FAPA is used as the inlet to a mass spectrometer.

Ionospheric response over Europe during the solar eclipse of March 20, 2015

NASA Astrophysics Data System (ADS)

Hoque, Mohammed Mainul; Wenzel, Daniela; Jakowski, Norbert; Gerzen, Tatjana; Berdermann, Jens; Wilken, Volker; Kriegel, Martin; Sato, Hiroatsu; Borries, Claudia; Minkwitz, David

2016-10-01

The solar eclipse on March 20, 2015 was a fascinating event for people in Northern Europe. From a scientific point of view, the solar eclipse can be considered as an in situ experiment on the Earth's upper atmosphere with a well-defined switching off and on of solar irradiation. Due to the strong changes in solar radiation during the eclipse, dynamic processes were initiated in the atmosphere and ionosphere causing a measurable impact, for example, on temperature and ionization. We analyzed the behavior of total ionospheric ionization over Europe by reconstructing total electron content (TEC) maps and differential TEC maps. Investigating the large depletion zone around the shadow spot, we found a TEC reduction of up to 6 TEC units, i.e., the total plasma depletion reached up to about 50%. However, the March 20, 2015 eclipse occurred during the recovery phase of a strong geomagnetic storm and the ionosphere was still perturbed and depleted. Therefore, the unusual high depletion is due to the negative bias of up to 20% already observed over Northern Europe before the eclipse occurred. After removing the negative storm effect, the eclipse-induced depletion amounts to about 30%, which is in agreement with previous observations. During the solar eclipse, ionospheric plasma redistribution processes significantly affected the shape of the electron density profile, which is seen in the equivalent slab thickness derived by combining vertical incidence sounding (VS) and TEC measurements. We found enhanced slab thickness values revealing, on the one hand, an increased width of the ionosphere around the maximum phase and, on the other, evidence for delayed depletion of the topside ionosphere. Additionally, we investigated very low frequency (VLF) signal strength measurements and found immediate amplitude changes due to ionization loss at the lower ionosphere during the eclipse time. We found that the magnitude of TEC depletion is linearly dependent on the Sun's obscuration function. By modelling TEC depletion and knowing the Sun's obscuration function in advance, Global Navigation Satellite System (GNSS) operators may improve the broadcast ionospheric correction during a solar eclipse day.

Analysis of anabolic steroids in urine by gas chromatography-microchip atmospheric pressure photoionization-mass spectrometry with chlorobenzene as dopant.

PubMed

Hintikka, Laura; Haapala, Markus; Kuuranne, Tiia; Leinonen, Antti; Kostiainen, Risto

2013-10-18

A gas chromatography-microchip atmospheric pressure photoionization-tandem mass spectrometry (GC-μAPPI-MS/MS) method was developed for the analysis of anabolic androgenic steroids in urine as their trimethylsilyl derivatives. The method utilizes a heated nebulizer microchip in atmospheric pressure photoionization mode (μAPPI) with chlorobenzene as dopant, which provides high ionization efficiency by producing abundant radical cations with minimal fragmentation. The performance of GC-μAPPI-MS/MS was evaluated with respect to repeatability, linearity, linear range, and limit of detection (LOD). The results confirmed the potential of the method for doping control analysis of anabolic steroids. Repeatability (RSD<10%), linearity (R(2)≥0.996) and sensitivity (LODs 0.05-0.1ng/mL) were acceptable. Quantitative performance of the method was tested and compared with that of conventional GC-electron ionization-MS, and the results were in good agreement. Copyright © 2013 Elsevier B.V. All rights reserved.

The method for on-site determination of trace concentrations of methyl mercaptan and dimethyl sulfide in air using a mobile mass spectrometer with atmospheric pressure chemical ionization, combined with a fast enrichment/separation system.

PubMed

Kudryavtsev, Andrey S; Makas, Alexey L; Troshkov, Mikhail L; Grachev, Mikhail А; Pod'yachev, Sergey P

2014-06-01

A method for fast simultaneous on-site determination of methyl mercaptan and dimethyl sulfide in air was developed. The target compounds were actively collected on silica gel, followed by direct flash thermal desorption, fast separation on a short chromatographic column and detection by means of mass spectrometer with atmospheric pressure chemical ionization. During the sampling of ambient air, water vapor was removed with a Nafion selective membrane. A compact mass spectrometer prototype, which was designed earlier at Trofimuk Institute of Petroleum Geology and Geophysics, was used. The minimization of gas load of the atmospheric pressure ion source allowed reducing the power requirements and size of the vacuum system and increasing its ruggedness. The measurement cycle is about 3 min. Detection limits in a 0.6 L sample are 1 ppb for methyl mercaptan and 0.2 ppb for dimethyl sulfide. Copyright © 2014 Elsevier B.V. All rights reserved.

Siphon flows in isolated magnetic flux tubes. V - Radiative flows with variable ionization

NASA Technical Reports Server (NTRS)

Montesinos, Benjamin; Thomas, John H.

1993-01-01

Steady siphon flows in arched isolated magnetic flux tubes in the solar atmosphere are calculated here including radiative transfer between the flux tube and its surrounding and variable ionization of the flowing gas. It is shown that the behavior of a siphon flow is strongly determined by the degree of radiative coupling between the flux tube and its surroundings in the superadiabatic layer just below the solar surface. Critical siphon flows with adiabatic tube shocks in the downstream leg are calculated, illustrating the radiative relaxation of the temperature jump downstream of the shock. For flows in arched flux tubes reaching up to the temperature minimum, where the opacity is low, the gas inside the flux tube is much cooler than the surrounding atmosphere at the top of the arch. It is suggested that gas cooled by siphon flows contribute to the cool component of the solar atmosphere at the height of the temperature minimum implied by observations of the infrared CO bands at 4.6 and 2.3 microns.

Magnetosphere-Ionosphere Energy Interchange in the Electron Diffuse Aurora

NASA Technical Reports Server (NTRS)

Khazanov, George V.; Glocer, Alex; Himwich, E. W.

2014-01-01

The diffuse aurora has recently been shown to be a major contributor of energy flux into the Earth's ionosphere. Therefore, a comprehensive theoretical analysis is required to understand its role in energy redistribution in the coupled ionosphere-magnetosphere system. In previous theoretical descriptions of precipitated magnetospheric electrons (E is approximately 1 keV), the major focus has been the ionization and excitation rates of the neutral atmosphere and the energy deposition rate to thermal ionospheric electrons. However, these precipitating electrons will also produce secondary electrons via impact ionization of the neutral atmosphere. This paper presents the solution of the Boltzman-Landau kinetic equation that uniformly describes the entire electron distribution function in the diffuse aurora, including the affiliated production of secondary electrons (E greater than 600 eV) and their ionosphere-magnetosphere coupling processes. In this article, we discuss for the first time how diffuse electron precipitation into the atmosphere and the associated secondary electron production participate in ionosphere-magnetosphere energy redistribution.

A Compact Ion and Neutral Mass Spectrometer for Measuring Atmospheric Composition with Preliminary Results from the Dellingr Mission

NASA Astrophysics Data System (ADS)

Jones, S.; Paschalidis, N.; Rodriguez, M.; Sittler, E. C., Jr.; Chornay, D. J.; Uribe, P.; Cameron, T.

2017-12-01

A compact Ion and Neutral Mass Spectrometer (INMS) has been developed for GSFC's Dellingr mission, using the 6U CubeSat platform. Dellingr is expected to deploy into ISS orbit in October 2017 to measure the dynamics of the ionosphere-thermosphere-mesosphere and to determine the steady state background atmospheric conditions at this altitude. The INMS makes in situ measurements of ionized and neutral H, He, N, O, N2, O2 densities with M/dM of approximately 10-12 for thermal particles. The INMS is based on particle acceleration, electronically gated time of flight (TOF), electrostatic analyzer, and CEM detectors. The compact instrument has a dual symmetric configuration with ion and neutral sensor heads on opposite sides of the shared electronics. The neutral front-end includes thermionic ionization and ion-blocking grids. The electronics include fast preamplifiers, electric gating, and TOF measurements and processing, C&DH digital electronics for commands, data storage and back-end I/O, and HVPS for detector and sensor biases. The data package includes 400 bins of mass spectra per ion and neutral sensor and key housekeeping and calibration data, in a single time tagged data frame of 14kbits uncompressed. The nominal data sampling is 1 sec corresponding to 7.5km spatial resolution in LEO orbits. This miniaturized instrument occupies a 1.1U volume, weighs only 570g and nominally operates at 1.2W. This presentation will include preliminary flight data of ions and neutrals from the Dellingr mission and outlines improvements incorporated into the design for the Dellingr (Oct 2017), ExoCube2 (Dec 2017) and petitSat (2020) CubeSat missions.

Dissociative recombination in planetary ionospheres

NASA Technical Reports Server (NTRS)

Fox, J. L.

1993-01-01

Ionization in planetary atmospheres can be produced by solar photoionization, photoelectron impact ionization, and, in auroral regions, by impact of precipitating particles. This ionization is lost mainly in dissociative recombination (DR) of molecular ions. Although atomic ions cannot undergo DR, they can be transformed locally through ion-molecule reactions into molecular ions, or they may be transported vertically or horizontally to regions of the atmosphere where such transformations are possible. Because DR reactions tend to be very exothermic, they can be an important source of kinetically or internally excited fragments. In interplanetary thermospheres, the neutral densities decrease exponentially with altitude. Below the homopause (or turbopause), the atmosphere is assumed to be throughly mixed by convection and/or turbulence. Above the homopause, diffusion is the major transport mechanism, and each species is distributed according to its mass, with the logarithmic derivative of the density with repect to altitude given approximately by -1/H, where H = kT/mg is the scale height. In this expression, T is the neutral temperature, g is the local acceleratiion of gravity, and m is the mass of the species. Thus lighter species become relatively more abundant, and heavier species less abundant, as the altitude increases. This variation of the neutral composition can lead to changes in the ion composition; furthermore, as the neutral densities decrease, dissociative recombination becomes more important relative to ion-neutral reactions as a loss mechanism for molecular ions.

Ionization in atmospheres of brown dwarfs and extrasolar planets VI: Properties of large-scale discharge events

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bailey, R. L.; Helling, Ch.; Hodosán, G.

2014-03-20

Mineral clouds in substellar atmospheres play a special role as a catalyst for a variety of charge processes. If clouds are charged, the surrounding environment becomes electrically activated, and ensembles of charged grains are electrically discharging (e.g., by lightning), which significantly influences the local chemistry creating conditions similar to those thought responsible for life in early planetary atmospheres. We note that such lightning discharges contribute also to the ionization state of the atmosphere. We apply scaling laws for electrical discharge processes from laboratory measurements and numerical experiments to DRIFT-PHOENIX model atmosphere results to model the discharge's propagation downward (as lightning)more » and upward (as sprites) through the atmospheric clouds. We evaluate the spatial extent and energetics of lightning discharges. The atmospheric volume affected (e.g., by increase of temperature or electron number) is larger in a brown dwarf atmosphere (10{sup 8}-10{sup 10} m{sup 3}) than in a giant gas planet (10{sup 4}-10{sup 6} m{sup 3}). Our results suggest that the total dissipated energy in one event is <10{sup 12} J for all models of initial solar metallicity. First attempts to show the influence of lightning on the local gas phase indicate an increase of small carbohydrate molecules like CH and CH{sub 2} at the expense of CO and CH{sub 4}. Dust-forming molecules are destroyed and the cloud particle properties are frozen in unless enough time is available for complete evaporation. We summarize instruments potentially suitable to observe lightning on extrasolar objects.« less

Measurement of HONO, HNCO, and other inorganic acids by negative-ion proton-transfer chemical-ionization mass spectrometry (NI-PT-CIMS): application to biomass burning emissions

Treesearch

J. M. Roberts; P. Veres; C. Warneke; J. A. Neuman; R. A. Washenfelder; S. S. Brown; M. Baasandorj; J. B. Burkholder; I. R. Burling; T. J. Johnson; R. J. Yokelson; J. de Gouw

2010-01-01

A negative-ion proton transfer chemical ionization mass spectrometric technique (NI-PT-CIMS), using acetate as the reagent ion, was applied to the measurement of volatile inorganic acids of atmospheric interest: hydrochloric (HCl), nitrous (HONO), nitric 5 (HNO3), and isocyanic (HNCO) acids. Gas phase calibrations through the sampling inlet showed the method to be...

Excitation and Ionization Cross Sections for Electron-Beam Energy Deposition in High Temperature Air

DTIC Science & Technology

1987-07-09

are given and compared to existing experimental results or other theoretical approaches. This information can readily be used as input for a deposition...of the doubly-differential, singly- differential and total ionization cross sections which subsequently served to guide theoretical calculations on...coworkers have been leaders in developing a theoretical base for studying electron production and energy deposition in atmospheric gases such as He, N2

Method of and system for producing electrical power

DOEpatents

Carabetta, Ralph A.; Staats, Gary E.; Cutting, John C.

1993-01-01

A method and system for converting the chemical energy of methane to electrical energy. Methane is thermally decomposed to hydrogen and carbon in a decomposing unit at a temperature not less than 1200.degree. K. and at a pressure above atmospheric pressure. Carbon and substantially pure oxygen and a cesium or potassium seed material is transmitted to a combustor which is maintained at a pressure of at least 50 atmospheres to combust the carbon and oxygen and provide an ionized plasma having a temperature not less than 2900.degree. K. The ionized plasma is accelerated to a velocity not less than 1000 m/sec and transported through an MHD generator having a magnetic field in the range of from 4 to 6 Tesla to generate dc power. The ionized plasma is decelerated and passed from the MHD generator in heat exchange relationship with the methane to heat the methane for decomposition, and thereafter any cesium or potassium seed material is recovered and transported to the combustor, and the dc power from the MHD generator is converted to ac power.

Method of and system for producing electrical power

DOEpatents

Carabetta, Ralph A.; Staats, Gary E.; Cutting, John C.

1993-01-01

A method and system for converting the chemical energy of methane to electrical energy. Methane is thermally decomposed to hydrogen and carbon in a decomposing unit at a temperature not less than about 1200.degree. K. and at a pressure at least slightly above atmospheric pressure. Carbon and substantially pure oxygen and a cesium or potassium seed material is transmitted to a combustor which is maintained at a pressure of at least about 50 atmospheres to combust the carbon and oxygen and provide an ionized plasma having a temperature not less than about 2800.degree. K. The ionized plasma is accelerated to a velocity not less than about 1000 m/sec and transported through an MHD generator having a magnetic field in the range of from about 4 to about 6 Tesla to generate dc power. The ionized plasma is de-accelerated and passed from the MHD generator in heat exchange relationship with the methane to heat same for decomposition and or reaction, and thereafter any cesium or potassium seed material is recovered and transported to the combustor, and the dc power from the MHD generator is converted to ac power.

Gas Chromatography-Tandem Mass Spectrometry of Lignin Pyrolyzates with Dopant-Assisted Atmospheric Pressure Chemical Ionization and Molecular Structure Search with CSI:FingerID

NASA Astrophysics Data System (ADS)

Larson, Evan A.; Hutchinson, Carolyn P.; Lee, Young Jin

2018-06-01

Dopant-assisted atmospheric pressure chemical ionization (dAPCI) is a soft ionization method rarely used for gas chromatography-mass spectrometry (GC-MS). The current study combines GC-dAPCI with tandem mass spectrometry (MS/MS) for analysis of a complex mixture such as lignin pyrolysis analysis. To identify the structures of volatile lignin pyrolysis products, collision-induced dissociation (CID) MS/MS using a quadrupole time-of-flight mass spectrometer (QTOFMS) and pseudo MS/MS through in-source collision-induced dissociation (ISCID) using a single stage TOFMS are utilized. To overcome the lack of MS/MS database, Compound Structure Identification (CSI):FingerID is used to interpret CID spectra and predict best matched structures from PubChem library. With this approach, a total of 59 compounds were positively identified in comparison to only 22 in NIST database search of GC-EI-MS dataset. This study demonstrates the effectiveness of GC-dAPCI-MS/MS to overcome the limitations of traditional GC-EI-MS analysis when EI-MS database is not sufficient. [Figure not available: see fulltext.

Development of a particle-trap preconcentration-soft ionization mass spectrometric technique for the quantification of mercury halides in air.

PubMed

Deeds, Daniel A; Ghoshdastidar, Avik; Raofie, Farhad; Guérette, Élise-Andrée; Tessier, Alain; Ariya, Parisa A

2015-01-01

Measurement of oxidized mercury, Hg(II), in the atmosphere poses a significant analytical challenge as Hg(II) is present at ultra-trace concentrations (picograms per cubic meter air). Current technologies are sufficiently sensitive to measure the total Hg present as Hg(II) but cannot determine the chemical speciation of Hg(II). We detail here the development of a soft ionization mass spectrometric technique coupled with preconcentration onto nano- or microparticle-based traps prior to analysis for the measurement of mercury halides in air. The current methodology has comparable detection limits (4-11 pg m(-3)) to previously developed techniques for the measurement of total inorganic mercury in air while allowing for the identification of HgX2 in collected samples. Both mercury chloride and mercury bromide have been sporadically detected in Montreal urban and indoor air using atmospheric pressure chemical ionization-mass spectrometry (APCI-MS). We discuss limitations and advantages of the current technique and discuss potential avenues for future research including quantitative trace measurements of a larger range of mercury compounds.

Detection of transient radical cations in electron transfer-initiated Diels-Alder reactions by electrospray ionization mass spectrometry.

PubMed

Fürmeier, Sven; Metzger, Jürgen O

2004-11-10

The coupling of a simple microreactor to an atmospheric pressure ion source, such as electrospray ionization (ESI) or atmospheric pressure chemical ionization (APCI), allows the investigation of reactions in solution by mass spectrometry. The tris(p-bromophenyl)aminium hexachloroantimonate (1(*)(+)SbCl(6)(-))-initiated reactions of phenylvinylsulfide (2) and cyclopentadiene (3) and of trans-anethole (5) and isoprene (6) and the dimerization of 1,3-cyclohexadiene (8) to give the respective Diels-Alder products were studied. These preparatively interesting reactions proceed as radical cation chain reactions via the transient radical cations of the respective dienophiles and of the respective Diels-Alder addition products. These radical cations could be detected directly and characterized unambiguously in the reacting solution by ESI-MS-MS. The identity was confirmed by comparison with MS-MS spectra of the authentic radical cations obtained by APCI-MS and by CID experiments of the corresponding molecular ions generated by EI-MS. In addition, substrates and products could be monitored easily in the reacting solution by APCI-MS.

Dynamic target ionization using an ultrashort pulse of a laser field

NASA Astrophysics Data System (ADS)

Makarov, D. N.; Matveev, V. I.; Makarova, K. A.

2014-09-01

Ionization processes under the interaction of an ultrashort pulse of an electromagnetic field with atoms in nonstationary states are considered. As an example, the ionization probability of the hydrogen-like atom upon the decay of quasi-stationary state is calculated. The method developed can be applied to complex systems, including targets in collisional states and various chemical reactions.

Ionizing radiation calculations and comparisons with LDEF data

NASA Technical Reports Server (NTRS)

Armstrong, T. W.; Colborn, B. L.; Watts, J. W., Jr.

1992-01-01

In conjunction with the analysis of LDEF ionizing radiation dosimetry data, a calculational program is in progress to aid in data interpretation and to assess the accuracy of current radiation models for future mission applications. To estimate the ionizing radiation environment at the LDEF dosimeter locations, scoping calculations for a simplified (one dimensional) LDEF mass model were made of the primary and secondary radiations produced as a function of shielding thickness due to trapped proton, galactic proton, and atmospheric (neutron and proton cosmic ray albedo) exposures. Preliminary comparisons of predictions with LDEF induced radioactivity and dose measurements were made to test a recently developed model of trapped proton anisotropy.

Desorption atmospheric pressure photoionization high-resolution mass spectrometry: a complementary approach for the chemical analysis of atmospheric aerosols.

PubMed

Parshintsev, Jevgeni; Vaikkinen, Anu; Lipponen, Katriina; Vrkoslav, Vladimir; Cvačka, Josef; Kostiainen, Risto; Kotiaho, Tapio; Hartonen, Kari; Riekkola, Marja-Liisa; Kauppila, Tiina J

2015-07-15

On-line chemical characterization methods of atmospheric aerosols are essential to increase our understanding of physicochemical processes in the atmosphere, and to study biosphere-atmosphere interactions. Several techniques, including aerosol mass spectrometry, are nowadays available, but they all suffer from some disadvantages. In this research, desorption atmospheric pressure photoionization high-resolution (Orbitrap) mass spectrometry (DAPPI-HRMS) is introduced as a complementary technique for the fast analysis of aerosol chemical composition without the need for sample preparation. Atmospheric aerosols from city air were collected on a filter, desorbed in a DAPPI source with a hot stream of toluene and nitrogen, and ionized using a vacuum ultraviolet lamp at atmospheric pressure. To study the applicability of the technique for ambient aerosol analysis, several samples were collected onto filters and analyzed, with the focus being on selected organic acids. To compare the DAPPI-HRMS data with results obtained by an established method, each filter sample was divided into two equal parts, and the second half of the filter was extracted and analyzed by liquid chromatography/mass spectrometry (LC/MS). The DAPPI results agreed with the measured aerosol particle number. In addition to the targeted acids, the LC/MS and DAPPI-HRMS methods were found to detect different compounds, thus providing complementary information about the aerosol samples. DAPPI-HRMS showed several important oxidation products of terpenes, and numerous compounds were tentatively identified. Thanks to the soft ionization, high mass resolution, fast analysis, simplicity and on-line applicability, the proposed methodology has high potential in the field of atmospheric research. Copyright © 2015 John Wiley & Sons, Ltd.

Flow Tube Studies of Gas Phase Chemical Processes of Atmospheric Importance

NASA Technical Reports Server (NTRS)

Molina, Mario J.

1997-01-01

The objective of this project is to conduct measurements of elementary reaction rate constants and photochemistry parameters for processes of importance in the atmosphere. These measurements are being carried out under temperature and pressure conditions covering those applicable to the stratosphere and upper troposphere, using the chemical ionization mass spectrometry turbulent flow technique developed in our laboratory.

Laser electrospray mass spectrometry of adsorbed molecules at atmospheric pressure

NASA Astrophysics Data System (ADS)

Brady, John J.; Judge, Elizabeth J.; Simon, Kuriakose; Levis, Robert J.

2010-02-01

Atmospheric pressure mass analysis of solid phase biomolecules is performed using laser electrospray mass spectrometry (LEMS). A non-resonant femtosecond duration laser pulse vaporizes native samples at atmospheric pressure for subsequent electrospray ionization and transfer into a mass spectrometer. LEMS was used to detect a complex molecule (irinotecan HCl), a complex mixture (cold medicine formulation with active ingredients: acetaminophen, dextromethorphan HBr and doxylamine succinate), and a biological building block (deoxyguanosine) deposited on steel surfaces without a matrix molecule.

Electrodynamic balance-mass spectrometry of single particles as a new platform for atmospheric chemistry research

NASA Astrophysics Data System (ADS)

Birdsall, Adam W.; Krieger, Ulrich K.; Keutsch, Frank N.

2018-01-01

New analytical techniques are needed to improve our understanding of the intertwined physical and chemical processes that affect the composition of aerosol particles in the Earth's atmosphere, such as gas-particle partitioning and homogenous or heterogeneous chemistry, and their ultimate relation to air quality and climate. We describe a new laboratory setup that couples an electrodynamic balance (EDB) to a mass spectrometer (MS). The EDB stores a single laboratory-generated particle in an electric field under atmospheric conditions for an arbitrarily long length of time. The particle is then transferred via gas flow to an ionization region that vaporizes and ionizes the analyte molecules before MS measurement. We demonstrate the feasibility of the technique by tracking evaporation of polyethylene glycol molecules and finding agreement with a kinetic model. Fitting data to the kinetic model also allows determination of vapor pressures to within a factor of 2. This EDB-MS system can be used to study fundamental chemical and physical processes involving particles that are difficult to isolate and study with other techniques. The results of such measurements can be used to improve our understanding of atmospheric particles.

Modeling of plasma chemical processes in the artificial ionized layer in the upper atmosphere by the nanosecond corona discharge

NASA Astrophysics Data System (ADS)

Vikharev, A. L.; Gorbachev, A. M.; Ivanov, O. A.; Kolisko, A. L.; Litvak, A. G.

1993-08-01

The plasma chemical processes in the corona discharge formed in air by a series of high voltage pulses of nanosecond duration are investigated experimentally. The experimental conditions (reduced electric field, duration and repetition frequency of the pulses, gas pressure in the chamber) modeled the regime of creation of the artificial ionized layer (AIL) in the upper atmosphere by a nanosecond microwave discharge. It was found that in a nanosecond microwave discharge predominantly generation of ozone occurs, and that the production of nitrogen dioxide is not large. The energy expenditures for the generation of one O 3 molecule were about 15 eV. On the basis of the experimental results the prognosis of the efficiency of ozone generation in AIL was made.

Theoretical determination of the ionization potential and the electron affinity of organic semiconductors

NASA Astrophysics Data System (ADS)

Yanagisawa, Susumu

2017-11-01

Ionization potential and electron affinity of organic semicondutors are important quantities, which are relevant to charge injection barriers. The electrostatic and dynamical contributions to the polarization energies for the injected charges in pentacene polymorphs were investigated. While the dynamical polarization induced narrowing of the energy gap, the electrostatic effect shifted up or down the frontier energy levels, which is sensitive to the molecular orientation at the surface.

Radar Detectability Studies of Slow and Small Zodiacal Dust Cloud Particles. III. The Role of Sodium and the Head Echo Size on the Probability of Detection

NASA Astrophysics Data System (ADS)

Janches, D.; Swarnalingam, N.; Carrillo-Sanchez, J. D.; Gomez-Martin, J. C.; Marshall, R.; Nesvorný, D.; Plane, J. M. C.; Feng, W.; Pokorný, P.

2017-07-01

We present a path forward on a long-standing issue concerning the flux of small and slow meteoroids, which are believed to be the dominant portion of the incoming meteoric mass flux into the Earth’s atmosphere. Such a flux, which is predicted by dynamical dust models of the Zodiacal Cloud, is not evident in ground-based radar observations. For decades this was attributed to the fact that the radars used for meteor observations lack the sensitivity to detect this population, due to the small amount of ionization produced by slow-velocity meteors. Such a hypothesis has been challenged by the introduction of meteor head echo (HE) observations with High Power and Large Aperture radars, in particular the Arecibo 430 MHz radar. Janches et al. developed a probabilistic approach to estimate the detectability of meteors by these radars and initially showed that, with the current knowledge of ablation and ionization, such particles should dominate the detected rates by one to two orders of magnitude compared to the actual observations. In this paper, we include results in our model from recently published laboratory measurements, which showed that (1) the ablation of Na is less intense covering a wider altitude range; and (2) the ionization probability, {β }{ip}, for Na atoms in the air is up to two orders of magnitude smaller for low speeds than originally believed. By applying these results and using a somewhat smaller size of the HE radar target we offer a solution that reconciles these observations with model predictions.

Radar Detectability Studies of Slow and Small Zodiacal Dust Cloud Particles. III. The Role of Sodium and the Head Echo Size on the Probability of Detection

NASA Technical Reports Server (NTRS)

Janches, D.; Swarnalingam, N.; Carrillo-Sanchez, J. D.; Gomez-Martin, J. C.; Marshall, R.; Nesvorny, D.; Plane, J. M. C.; Feng, W.; Pokorny, P.

2017-01-01

We present a path forward on a long-standing issue concerning the flux of small and slow meteoroids, which are believed to be the dominant portion of the incoming meteoric mass flux into the Earth's atmosphere. Such a flux, which is predicted by dynamical dust models of the Zodiacal Cloud, is not evident in ground-based radar observations. For decades this was attributed to the fact that the radars used for meteor observations lack the sensitivity to detect this population, due to the small amount of ionization produced by slow-velocity meteors. Such a hypothesis has been challenged by the introduction of meteor head echo (HE) observations with High Power and Large Aperture radars, in particular the Arecibo 430 MHz radar. Janches et al. developed a probabilistic approach to estimate the detectability of meteors by these radars and initially showed that, with the current knowledge of ablation and ionization, such particles should dominate the detected rates by one to two orders of magnitude compared to the actual observations. In this paper, we include results in our model from recently published laboratory measurements, which showed that (1) the ablation of Na is less intense covering a wider altitude range; and (2) the ionization probability, Beta ip, for Na atoms in the air is up to two orders of magnitude smaller for low speeds than originally believed. By applying these results and using a somewhat smaller size of the HE radar target we offer a solution that reconciles these observations with model predictions.

On- and off-axis spectral emission features from laser-produced gas breakdown plasmas

NASA Astrophysics Data System (ADS)

Harilal, S. S.; Skrodzki, P. J.; Miloshevsky, A.; Brumfield, B. E.; Phillips, M. C.; Miloshevsky, G.

2017-06-01

Laser-heated gas breakdown plasmas or sparks emit profoundly in the ultraviolet and visible region of the electromagnetic spectrum with contributions from ionic, atomic, and molecular species. Laser created kernels expand into a cold ambient with high velocities during their early lifetime followed by confinement of the plasma kernel and eventually collapse. However, the plasma kernels produced during laser breakdown of gases are also capable of exciting and ionizing the surrounding ambient medium. Two mechanisms can be responsible for excitation and ionization of the surrounding ambient: photoexcitation and ionization by intense ultraviolet emission from the sparks produced during the early times of their creation and/or heating by strong shocks generated by the kernel during its expansion into the ambient. In this study, an investigation is made on the spectral features of on- and off-axis emission of laser-induced plasma breakdown kernels generated in atmospheric pressure conditions with an aim to elucidate the mechanisms leading to ambient excitation and emission. Pulses from an Nd:YAG laser emitting at 1064 nm with a pulse duration of 6 ns are used to generate plasma kernels. Laser sparks were generated in air, argon, and helium gases to provide different physical properties of expansion dynamics and plasma chemistry considering the differences in laser absorption properties, mass density, and speciation. Point shadowgraphy and time-resolved imaging were used to evaluate the shock wave and spark self-emission morphology at early and late times, while space and time resolved spectroscopy is used for evaluating the emission features and for inferring plasma physical conditions at on- and off-axis positions. The structure and dynamics of the plasma kernel obtained using imaging techniques are also compared to numerical simulations using the computational fluid dynamics code. The emission from the kernel showed that spectral features from ions, atoms, and molecules are separated in time with early time temperatures and densities in excess of 35 000 K and 4 × 1018/cm3 with an existence of thermal equilibrium. However, the emission from the off-kernel positions from the breakdown plasmas showed enhanced ultraviolet radiation with the presence of N2 bands and is represented by non-local thermodynamic equilibrium (non-LTE) conditions. Our results also highlight that the ultraviolet radiation emitted during the early time of spark evolution is the predominant source of the photo-excitation of the surrounding medium.

On- and off-axis spectral emission features from laser-produced gas breakdown plasmas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Harilal, S. S.; Skrodzki, P. J.; Miloshevsky, A.

Laser-heated gas breakdown plasmas or sparks emit profoundly in the ultraviolet and visible region of the electromagnetic spectrum with contributions from ionic, atomic, and molecular species. Laser created kernels expand into a cold ambient with high velocities during its early lifetime followed by confinement of the plasma kernel and eventually collapse. However, the plasma kernels produced during laser breakdown of gases are also capable of exciting and ionizing the surrounding ambient medium. Two mechanisms can be responsible for excitation and ionization of surrounding ambient: viz. photoexcitation and ionization by intense ultraviolet emission from the sparks produced during the early timesmore » of its creation and/or heating by strong shocks generated by the kernel during its expansion into the ambient. In this study, an investigation is made on the spectral features of on- and off-axis emission features of laser-induced plasma breakdown kernels generated in atmospheric pressure conditions with an aim to elucidate the mechanisms leading to ambient excitation and emission. Pulses from an Nd:YAG laser emitting at 1064 nm with 6 ns pulse duration are used to generate plasma kernels. Laser sparks were generated in air, argon, and helium gases to provide different physical properties of expansion dynamics and plasma chemistry considering the differences in laser absorption properties, mass density and speciation. Point shadowgraphy and time-resolved imaging were used to evaluate the shock wave and spark self-emission morphology at early and late times while space and time resolved spectroscopy is used for evaluating the emission features as well as for inferring plasma fundaments at on- and off-axis. Structure and dynamics of the plasma kernel obtained using imaging techniques are also compared to numerical simulations using computational fluid dynamics code. The emission from the kernel showed that spectral features from ions, atoms and molecules are separated in time with an early time temperatures and densities in excess of 35000 K and 4×10 18 /cm 3 with an existence of thermal equilibrium. However, the emission from the off-kernel positions from the breakdown plasmas showed enhanced ultraviolet radiation with the presence of N 2 bands and represented by non-LTE conditions. Finally, our results also highlight that the ultraviolet radiation emitted during early time of spark evolution is the predominant source of the photo-excitation of the surrounding medium.« less

On- and off-axis spectral emission features from laser-produced gas breakdown plasmas

DOE PAGES

Harilal, S. S.; Skrodzki, P. J.; Miloshevsky, A.; ...

2017-06-01

Laser-heated gas breakdown plasmas or sparks emit profoundly in the ultraviolet and visible region of the electromagnetic spectrum with contributions from ionic, atomic, and molecular species. Laser created kernels expand into a cold ambient with high velocities during its early lifetime followed by confinement of the plasma kernel and eventually collapse. However, the plasma kernels produced during laser breakdown of gases are also capable of exciting and ionizing the surrounding ambient medium. Two mechanisms can be responsible for excitation and ionization of surrounding ambient: viz. photoexcitation and ionization by intense ultraviolet emission from the sparks produced during the early timesmore » of its creation and/or heating by strong shocks generated by the kernel during its expansion into the ambient. In this study, an investigation is made on the spectral features of on- and off-axis emission features of laser-induced plasma breakdown kernels generated in atmospheric pressure conditions with an aim to elucidate the mechanisms leading to ambient excitation and emission. Pulses from an Nd:YAG laser emitting at 1064 nm with 6 ns pulse duration are used to generate plasma kernels. Laser sparks were generated in air, argon, and helium gases to provide different physical properties of expansion dynamics and plasma chemistry considering the differences in laser absorption properties, mass density and speciation. Point shadowgraphy and time-resolved imaging were used to evaluate the shock wave and spark self-emission morphology at early and late times while space and time resolved spectroscopy is used for evaluating the emission features as well as for inferring plasma fundaments at on- and off-axis. Structure and dynamics of the plasma kernel obtained using imaging techniques are also compared to numerical simulations using computational fluid dynamics code. The emission from the kernel showed that spectral features from ions, atoms and molecules are separated in time with an early time temperatures and densities in excess of 35000 K and 4×1018 /cm3 with an existence of thermal equilibrium. However, the emission from the off-kernel positions from the breakdown plasmas showed enhanced ultraviolet radiation with the presence of N2 bands and represented by non-LTE conditions. Our results also highlight that the ultraviolet radiation emitted during early time of spark evolution is the predominant source of the photo-excitation of the surrounding medium.« less

Photoionization Modeling

NASA Technical Reports Server (NTRS)

Kallman, T.

2010-01-01

Warm absorber spectra are characterized by the many lines from partially ionized intermediate-Z elements, and iron, detected with the grating instruments on Chandra and XMM-Newton. If these ions are formed in a gas which is in photoionization equilibrium, they correspond to a broad range of ionization parameters, although there is evidence for certain preferred values. A test for any dynamical model for these outflows is to reproduce these properties, at some level of detail. In this paper we present a statistical analysis of the ionization distribution which can be applied both the observed spectra and to theoretical models. As an example, we apply it to our dynamical models for warm absorber outflows, based on evaporation from the molecular torus.

Dependence with air density of the response of the PTW SourceCheck ionization chamber for low energy brachytherapy sources.

PubMed

Tornero-López, Ana M; Guirado, Damián; Perez-Calatayud, Jose; Ruiz-Arrebola, Samuel; Simancas, Fernando; Gazdic-Santic, Maja; Lallena, Antonio M

2013-12-01

Air-communicating well ionization chambers are commonly used to assess air kerma strength of sources used in brachytherapy. The signal produced is supposed to be proportional to the air density within the chamber and, therefore, a density-independent air kerma strength is obtained when the measurement is corrected to standard atmospheric conditions using the usual temperature and pressure correction factor. Nevertheless, when assessing low energy sources, the ionization chambers may not fulfill that condition and a residual density dependence still remains after correction. In this work, the authors examined the behavior of the PTW 34051 SourceCheck ionization chamber when measuring the air kerma strength of (125)I seeds. Four different SourceCheck chambers were analyzed. With each one of them, two series of measurements of the air kerma strength for (125)I selectSeed(TM) brachytherapy sources were performed inside a pressure chamber and varying the pressure in a range from 747 to 1040 hPa (560 to 780 mm Hg). The temperature and relative humidity were kept basically constant. An analogous experiment was performed by taking measurements at different altitudes above sea level. Contrary to other well-known ionization chambers, like the HDR1000 PLUS, in which the temperature-pressure correction factor overcorrects the measurements, in the SourceCheck ionization chamber they are undercorrected. At a typical atmospheric situation of 933 hPa (700 mm Hg) and 20 °C, this undercorrection turns out to be 1.5%. Corrected measurements show a residual linear dependence on the density and, as a consequence, an additional density dependent correction must be applied. The slope of this residual linear density dependence is different for each SourceCheck chamber investigated. The results obtained by taking measurements at different altitudes are compatible with those obtained with the pressure chamber. Variations of the altitude and changes in the weather conditions may produce significant density corrections, and that effect should be taken into account. This effect is chamber-dependent, indicating that a specific calibration is necessary for each particular chamber. To our knowledge, this correction has not been considered so far for SourceCheck ionization chambers, but its magnitude cannot be neglected in clinical practice. The atmospheric pressure and temperature at which the chamber was calibrated need to be taken into account, and they should be reported in the calibration certificate. In addition, each institution should analyze the particular response of its SourceCheck ionization chamber and compute the adequate correction factors. In the absence of a suitable pressure chamber, a possibility for this assessment is to take measurements at different altitudes, spanning a wide enough air density range.

Dependence with air density of the response of the PTW SourceCheck ionization chamber for low energy brachytherapy sources

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tornero-López, Ana M.; Guirado, Damián; Ruiz-Arrebola, Samuel

2013-12-15

Purpose: Air-communicating well ionization chambers are commonly used to assess air kerma strength of sources used in brachytherapy. The signal produced is supposed to be proportional to the air density within the chamber and, therefore, a density-independent air kerma strength is obtained when the measurement is corrected to standard atmospheric conditions using the usual temperature and pressure correction factor. Nevertheless, when assessing low energy sources, the ionization chambers may not fulfill that condition and a residual density dependence still remains after correction. In this work, the authors examined the behavior of the PTW 34051 SourceCheck ionization chamber when measuring themore » air kerma strength of {sup 125}I seeds.Methods: Four different SourceCheck chambers were analyzed. With each one of them, two series of measurements of the air kerma strength for {sup 125}I selectSeed{sup TM} brachytherapy sources were performed inside a pressure chamber and varying the pressure in a range from 747 to 1040 hPa (560 to 780 mm Hg). The temperature and relative humidity were kept basically constant. An analogous experiment was performed by taking measurements at different altitudes above sea level.Results: Contrary to other well-known ionization chambers, like the HDR1000 PLUS, in which the temperature-pressure correction factor overcorrects the measurements, in the SourceCheck ionization chamber they are undercorrected. At a typical atmospheric situation of 933 hPa (700 mm Hg) and 20 °C, this undercorrection turns out to be 1.5%. Corrected measurements show a residual linear dependence on the density and, as a consequence, an additional density dependent correction must be applied. The slope of this residual linear density dependence is different for each SourceCheck chamber investigated. The results obtained by taking measurements at different altitudes are compatible with those obtained with the pressure chamber.Conclusions: Variations of the altitude and changes in the weather conditions may produce significant density corrections, and that effect should be taken into account. This effect is chamber-dependent, indicating that a specific calibration is necessary for each particular chamber. To our knowledge, this correction has not been considered so far for SourceCheck ionization chambers, but its magnitude cannot be neglected in clinical practice. The atmospheric pressure and temperature at which the chamber was calibrated need to be taken into account, and they should be reported in the calibration certificate. In addition, each institution should analyze the particular response of its SourceCheck ionization chamber and compute the adequate correction factors. In the absence of a suitable pressure chamber, a possibility for this assessment is to take measurements at different altitudes, spanning a wide enough air density range.« less

High-field asymmetric waveform ion mobility spectrometry for mass spectrometry-based proteomics.

PubMed

Swearingen, Kristian E; Moritz, Robert L

2012-10-01

High-field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve the detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, the authors review recent developments in LC-FAIMS-MS and its application to MS-based proteomics.

A pseudoatom in a cage: trimetallofullerene Y(3)@C(80) mimics y(3)n@c(80) with nitrogen substituted by a pseudoatom.

PubMed

Popov, Alexey A; Zhang, Lin; Dunsch, Lothar

2010-02-23

Y(3)C(80) obtained in the synthesis of nitride clusterfullerenes Y(3)N@C(2n) (2n = 80-88) by the reactive atmosphere method is found to be a genuine trimetallofullerene, Y(3)@C(80), with low ionization potential and divalent state of yttrium atoms. DFT studies of the electronic structure of Y(3)@C(80) show that this molecule mimics Y(3)N@C(80) with the pseudoatom (PA) instead of the nitrogen atom. Topology analysis of the electron density and electron localization function show that yttrium atoms form Y-PA bonds rather than direct Y-Y bonds. Molecular dynamics simulations show that the Y(3)PA cluster is as rigid as Y(3)N and rotates inside the fullerene cage as a single entity.

Structure and dynamics of the ionosphere. [Venus atmosphere

NASA Technical Reports Server (NTRS)

Nagy, A. F.; Brace, L. H.

1982-01-01

The structure of the Venus ionosphere and the major processes occurring within it are summarized. The daytime ionosphere is created by solar EUV radiation incident on the thermosphere; it is in photochemical equilibrium near its peak at about 142 km, where O2(+) is the major ion, and near diffusive equilibrium in its upper regions, where the major ion is O(+). The day-to-night plasma pressure gradient across the terminator drives a nightward ion flow which, together with electron precipitation, contributes to the formation of the nighttime ionosphere. Large-scale radial holes or plasma depletions extending downwards to nearly the ionization peak in the antisolar region are also observed which are associated with regions of strong radial magnetic fields. The ionopause is a highly dynamic and complex surface, extending from an average altitude of 290 km at the subsolar point to about 1000 km at the terminator and from 200 to over 3000 km on the nightside. A variety of solar wind interaction products are observed in the mantle, a transition region between the ionospheric plasma and the flowing shocked solar wind.

Dynamics of the upper middle atmosphere (80-110 km) at Tromsoe, June-December 1987, using the Tromsoe/Saskatoon M.F. radar

NASA Technical Reports Server (NTRS)

Manson, A. H.; Meek, C. E.

1989-01-01

A real time winds (RTW) system from Saskatoon operated with the Tromsoe M.F. (partial reflection) radar on a continuous basis, June to December 1987. Profiles with 3 km resolution were obtained every 5 minutes with weak ionization, and few geomagnetic disturbances limited the observations normally to 80 to 110 km. However, daily mean winds, tidal characteristics (24, 12 h) such as amplitudes, phases and wavelengths, and gravity wave characteristics (intensities, mean directions) are available throughout this interval, which includes MAC-SINE and Epsilon. This is particularly valuable in defining the background state for some experiments, e.g., rockets, and for comparison with related parameters from the lidar and other radars (EISCAT, SOUSY-VHF). Comparisons with dynamical parameters from Saskatoon (52 N) are made: the zonal circulation was weaker at Tromsoe, tidal amplitudes smaller, and summer 12 h tidal wavelengths shorter (approx. 80 km vs approx. 100 km). The fall transition for this tide occurred in September, earlier than observed elsewhere. Initial comparisons with other experimental systems are also made.

Luminescent tunable polydots: Charge effects in confined geometry

DOE PAGES

Wijesinghe, Sidath; Maskey, Sabina; Perahia, Dvora; ...

2017-06-28

Long-lived soft nanoparticles, formed by conjugated polymers, constitute a new class of far-from-equilibrium responsive structures for nano-medicine. Tethering ionizable groups to the polymers enables functionality. However concurrently, the ionic groups perturb the delicate balance of interactions that governs these particles. Using fully atomistic molecular dynamics simulations, this study probed the effects of charged groups tethered to poly para phenylene ethynylene substituted by alkyl groups on the polymer conformation and dynamics in confined geometry. As a result, we find that the ionizable groups affect the entire shape of the polydots and impact the conformation and dynamics of the polymer.

AmPMS: Detection of Ammonia and Amines in Particle Formation and Growth Experiments

NASA Astrophysics Data System (ADS)

Hanson, D. R.; McMurry, P. H.; Jiang, J.; Huey, L. G.; Tanner, D.

2010-12-01

Ammonia and amine compounds in the atmosphere can be a significant component of atmospheric aerosol. Theoretical work shows that these compounds have a potentially large affinity for the particulate phase if strong acids are present. The co-accumulation of amines/ammonia with acids on atmospheric particles can be important for growth of atmospheric particles. Also, the role of nitrogen bases in nucleation is believed to be important. While proton transfer mass spectrometry (MS) has been deployed to detect a wide variety of volatile organic compounds in the atmosphere using H3O+ as the ionizing agent, they are generally operated at reduced pressures of 0.002 to 0.01 atm, which can limit the ability to detect pptv levels of amines. Use of this technique at atmospheric pressure can increase its sensitivity, as demonstrated by the efficient detection of ammonia via proton transfer at ambient pressures and relative humidities in the lab [1]. An instrument based on this system was deployed in the field (NCCN 2009, Atlanta) and was recently connected to a chamber at the University of Minnesota where nucleation experiments involving sulfuric acid and amines were carried out. This instrument, Ambient pressure Proton transfer Mass Spectrometer (AmP-MS), combines the specificity of chemical ionization with the high sensitivity of atmospheric pressure ionization techniques. It works for species that have high proton affinities and it is relatively insensitive to highly abundant VOCs such as methanol, acetaldehyde, acetone, etc. Water-proton clusters are electrostatically drawn across a flow of analyte gas resulting in ion-molecule reaction times of ~0.5-to-1 ms, and sensitivities in the few Hz per pptv are possible. In the laboratory, ion-molecule reactions of water proton and water ammonium clusters with various amine species are facile [2] and Sunner et al. [3] showed that species with high gas-phase basicities, and thus high PAs, also react fast with highly hydrated H3O+ and NH4+ ions. Amines have large proton affinities. The basics of the AmP-MS construction and operation will be presented as well as data from its deployment in the field and from the laboratory chamber experiments. Focus will be on the veracity of the technique and on correlations of measurements with environmental conditions, particle size distributions, and sulfuric acid cluster measurements. Candidates for important roles in nucleation will be discussed. [1] Hanson, D.R., E. Kosciuch, The NH3 mass accommodation coefficient for uptake onto sulfuric acid solutions, J. Phys. Chem. A, 2003, 107, 2199-2208. [2] Viggiano, A. A., Dale, F., and Paulson, J. F.: Proton transfer reactions of H+(H2O)n=2-11 with methanol, ammonia, pyridine, acetonitrile and acetone, J. Chem. Phys., 88, 2469-2477, 1988. [3] Sunner J., G. Nicol, and P. Kebarle, Factors Determining Relative Sensitivity of Analytes in Positive Mode Atmospheric Pressure Ionization Mass Spectrometry, Anal. Chem. 1988, 60, 1300-1307.

Photoelectron imaging of doped helium nanodroplets

NASA Astrophysics Data System (ADS)

Neumark, Daniel

2008-03-01

Photoelectron images of helium nanodroplets doped with Kr and Ne atoms are reported. The images and resulting photoelectron spectra were obtained using tunable synchrotron radiation to ionize the droplets. Droplets were excited at 21.6 eV, corresponding to a strong droplet electronic excitation. The rare gas dopant is then ionized via a Penning excitation transfer process. The electron kinetic energy distributions reflect complex ionization and electron escape dynamics.

Terrestrial effects of high energy cosmic rays

NASA Astrophysics Data System (ADS)

Atri, Dimitra

On geological timescales, the Earth is likely to be exposed to higher than the usual flux of high energy cosmic rays (HECRs) from astrophysical sources such as nearby supernovae, gamma ray bursts or by galactic shocks. These high-energy particles strike the Earth's atmosphere, initiating an extensive air shower. As the air shower propagates deeper, it ionizes the atmosphere by producing charged secondary particles and photons. Increased ionization leads to changes in atmospheric chemistry, resulting in ozone depletion. This increases the flux of solar UVB radiation at the surface, which is potentially harmful to living organisms. Increased ionization affects the global electrical circuit, which could enhance the low-altitude cloud formation rate. Secondary particles such as muons and thermal neutrons produced as a result of hadronic interactions of the primary cosmic rays with the atmosphere are able to reach the ground, enhancing the biological radiation dose. The muon flux dominates the radiation dose from cosmic rays causing damage to DNA and an increase in mutation rates and cancer, which can have serious biological implications for surface and sub-surface life. Using CORSIKA, we perform massive computer simulations and construct lookup tables for 10 GeV - 1 PeV primaries, which can be used to quantify these effects from enhanced cosmic ray exposure to any astrophysical source. These tables are freely available to the community and can be used for other studies. We use these tables to study the terrestrial implications of galactic shock generated by the infall of our galaxy toward the Virgo cluster. Increased radiation dose from muons could be a possible mechanism explaining the observed periodicity in biodiversity in paleobiology databases.

Toward single-cell analysis by plume collimation in laser ablation electrospray ionization mass spectrometry.

PubMed

Stolee, Jessica A; Vertes, Akos

2013-04-02

Ambient ionization methods for mass spectrometry have enabled the in situ and in vivo analysis of biological tissues and cells. When an etched optical fiber is used to deliver laser energy to a sample in laser ablation electrospray ionization (LAESI) mass spectrometry, the analysis of large single cells becomes possible. However, because in this arrangement the ablation plume expands in three dimensions, only a small portion of it is ionized by the electrospray. Here we show that sample ablation within a capillary helps to confine the radial expansion of the plume. Plume collimation, due to the altered expansion dynamics, leads to greater interaction with the electrospray plume resulting in increased ionization efficiency, reduced limit of detection (by a factor of ~13, reaching 600 amol for verapamil), and extended dynamic range (6 orders of magnitude) compared to conventional LAESI. This enhanced sensitivity enables the analysis of a range of metabolites from small cell populations and single cells in the ambient environment. This technique has the potential to be integrated with flow cytometry for high-throughput metabolite analysis of sorted cells.

Dynamics of tunneling ionization using Bohmian mechanics

NASA Astrophysics Data System (ADS)

Douguet, Nicolas; Bartschat, Klaus

2018-01-01

Recent attoclock experiments and theoretical studies regarding the strong-field ionization of atoms by few-cycle infrared pulses revealed features that have attracted much attention. Here we investigate tunneling ionization and the dynamics of the electron probability using Bohmian mechanics. We consider a one-dimensional problem to illustrate the underlying mechanisms of the ionization process. It is revealed that in the major part of the below-the-barrier ionization regime, in an intense and short infrared pulse, the electron does not tunnel through the entire barrier, but rather starts already from the classically forbidden region. Moreover, we highlight the correspondence between the probability of locating the electron at a particular initial position and its asymptotic momentum. Bohmian mechanics also provides a natural definition of mean tunneling time and exit position, taking account of the time dependence of the barrier. Finally, we find that the electron can exit the barrier with significant kinetic energy, thereby corroborating the results of a recent study [N. Camus et al., Phys. Rev. Lett. 119, 023201 (2017), 10.1103/PhysRevLett.119.023201].

Quantitative correlations between collision induced dissociation mass spectrometry coupled with electrospray ionization or atmospheric pressure chemical ionization mass spectrometry - Experiment and theory

NASA Astrophysics Data System (ADS)

Ivanova, Bojidarka; Spiteller, Michael

2018-04-01

The problematic that we consider in this paper treats the quantitative correlation model equations between experimental kinetic and thermodynamic parameters of coupled electrospray ionization (ESI) mass spectrometry (MS) or atmospheric pressure chemical ionization (APCI) mass spectrometry with collision induced dissociation mass spectrometry, accounting for the fact that the physical phenomena and mechanisms of ESI- and APCI-ion formation are completely different. There are described forty two fragment reactions of three analytes under independent ESI- and APCI-measurements. The developed new quantitative models allow us to study correlatively the reaction kinetics and thermodynamics using the methods of mass spectrometry, which complementary application with the methods of the quantum chemistry provide 3D structural information of the analytes. Both static and dynamic quantum chemical computations are carried out. The object of analyses are [2,3-dimethyl-4-(4-methyl-benzoyl)-2,3-di-p-tolyl-cyclobutyl]-p-tolyl-methanone (1) and the polycyclic aromatic hydrocarbons derivatives of dibenzoperylen (2) and tetrabenzo [a,c,fg,op]naphthacene (3), respectively. As far as (1) is known to be a product of [2π+2π] cycloaddition reactions of chalcone (1,3-di-p-tolyl-propenone), however producing cyclic derivatives with different stereo selectivity, so that the study provide crucial data about the capability of mass spectrometry to provide determine the stereo selectivity of the analytes. This work also first provides quantitative treatment of the relations '3D molecular/electronic structures'-'quantum chemical diffusion coefficient'-'mass spectrometric diffusion coefficient', thus extending the capability of the mass spectrometry for determination of the exact 3D structure of the analytes using independent measurements and computations of the diffusion coefficients. The determination of the experimental diffusion parameters is carried out within the 'current monitoring method' evaluating the translation diffusion of charged analytes, while the theoretical modelling of MS ions and computations of theoretical diffusion coefficients are based on the Arrhenius type behavior of the charged species under ESI- and APCI-conditions. Although the study provide certain sound considerations for the quantitative relations between the reaction kinetic-thermodynamics and 3D structure of the analytes together with correlations between 3D molecular/electronic structures-quantum chemical diffusion coefficient-mass spectrometric diffusion coefficient, which contribute significantly to the structural analytical chemistry, the results have importance to other areas such as organic synthesis and catalysis as well.

Short-pulse lasers for weather control

NASA Astrophysics Data System (ADS)

Wolf, J. P.

2018-02-01

Filamentation of ultra-short TW-class lasers recently opened new perspectives in atmospheric research. Laser filaments are self-sustained light structures of 0.1–1 mm in diameter, spanning over hundreds of meters in length, and producing a low density plasma (1015–1017 cm‑3) along their path. They stem from the dynamic balance between Kerr self-focusing and defocusing by the self-generated plasma and/or non-linear polarization saturation. While non-linearly propagating in air, these filamentary structures produce a coherent supercontinuum (from 230 nm to 4 µm, for a 800 nm laser wavelength) by self-phase modulation (SPM), which can be used for remote 3D-monitoring of atmospheric components by Lidar (Light Detection and Ranging). However, due to their high intensity (1013–1014 W cm‑2), they also modify the chemical composition of the air via photo-ionization and photo-dissociation of the molecules and aerosols present in the laser path. These unique properties were recently exploited for investigating the capability of modulating some key atmospheric processes, like lightning from thunderclouds, water vapor condensation, fog formation and dissipation, and light scattering (albedo) from high altitude clouds for radiative forcing management. Here we review recent spectacular advances in this context, achieved both in the laboratory and in the field, reveal their underlying mechanisms, and discuss the applicability of using these new non-linear photonic catalysts for real scale weather control.

The Behavior of Systems in the Space Environment

DTIC Science & Technology

1991-07-19

Environment edited by Robert N. DeWitt U.S. Department of Energy , Washington, D.C., U.S.A. Dwight Duston Strategic Defense Initiative Organization, The...originates in a thin layer of the solar chromosphere, contains most of the solar energy in the extreme ultraviolet, but it cannot ionize any major...constituents of the atmosphere, whereas Lyman alpha can ionize only the trace of’nitric oxide. Virtually all the energy delivered in Lyman alpha is dissipated

AIRBORNE RADIATION DETECTOR

DOEpatents

Cartmell, T.R.; Gifford, J.F.

1959-08-01

An ionization chamber used for measuring the radioactivity of dust present in atmospheric air is described. More particularly. the patent describes a device comprising two concentric open ended, electrically connected cylinders between which is disposed a wire electrcde. A heating source is disposed inside of the cylinder to circulate air through the space between the two cylinders by convective flow. A high voltage electric field between the wire electrcde of the electrically connected cylinder will cause ionization of the air as it passes therethrough.

Analysis of Biomolecules by Atmospheric Pressure Visible-Wavelength MALDI-Ion Trap-MS in Transmission Geometry

NASA Astrophysics Data System (ADS)

West, Raymond E.; Findsen, Eric W.; Isailovic, Dragan

2013-10-01

We report the development of a new AP visible-wavelength MALDI-ion trap-MS instrument with significantly improved performance over our previously reported system ( Int. J. Mass Spectrom. 315, 66-73 (2012)). A Nd:YAG pulsed laser emitting light at 532 nm was used to desorb and ionize oligosaccharides and peptides in transmission geometry through a glass slide. Limits of detection (LODs) achieved in MS mode correspond to picomole quantities of oligosaccharides and femtomole quantities of peptides. Tandem MS (MS/MS) experiments enabled identification of enzymatically digested proteins and oligosaccharides by comparison of MS/MS spectra with data found in protein and glycan databases. Moreover, the softness of ionization, LODs, and fragmentation spectra of biomolecules by AP visible-wavelength MALDI-MS were compared to those obtained by AP UV MALDI-MS using a Nd:YAG laser emitting light at 355 nm. AP visible-wavelength MALDI appears to be a softer ionization technique then AP UV MALDI for the analysis of sulfated peptides, while visible-wavelength MALDI-MS, MS/MS, and MS/MS/MS spectra of other biomolecules analyzed were mostly similar to those obtained by AP UV MALDI-MS. Therefore, the methodology presented will be useful for MS and MSn analyses of biomolecules at atmospheric pressure. Additionally, the AP visible-wavelength MALDI developed can be readily used for soft ionization of analytes on various mass spectrometers.

Photo-triggering and secondary electron produced ionization in electric discharge ArF* excimer lasers

NASA Astrophysics Data System (ADS)

Xiong, Zhongmin; Kushner, Mark J.

2011-10-01

Electric discharge excimer lasers are sustained in multi-atmosphere attaching gas mixtures that are typically preionized to enable a reproducible, uniform glow, which maximizes optical quality and gain. This preionization is often accomplished using UV light produced by a corona discharge within the plasma cavity. To quantify the relationship between corona discharge properties and those of the laser discharge, the triggering of electron avalanche by preionizing UV light in an electric discharge-pumped ArF* excimer laser was numerically investigated using a two-dimensional model. The preionizing UV fluxes were generated by a corona-bar discharge driven by the same voltage pulse as the main discharge sustained in a multi-atmospheric Ne/Ar/Xe/F2 gas mixture. The resulting peak photo-electron density in the inter-electrode spacing is around 108 cm-3, and its distribution is biased toward the UV source. The preionization density increases with increasing dielectric constant and capacitance of the corona bar. The symmetry and uniformity of the discharge are, however, improved significantly once the main avalanche develops. In addition to bulk electron impact ionization, the ionization generated by sheath accelerated secondary electrons was found to be important in sustaining the discharge current at experimentally observed values. At peak current, the magnitude of the ionization by sheath accelerated electrons is comparable to that from bulk electron impact in the vicinity of the cathode.

Atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry of friction modifier additives analyzed directly from base oil solutions.

PubMed

Widder, Lukas; Brennerb, Josef; Huttera, Herbert

2014-01-01

To develop new products and to apply measures of quality control quick and simple accessibility of additive composition in automo- tive lubrication is important. The aim of this study was to investigate the possibility of analyzing organic friction modifier additives by means of atmospheric pressure matrix-assisted laser desorption/ionization mass spectrometry [AP-MALDI-MS] from lubricant solu- tions without the use of additional separation techniques. Analyses of selected friction modifier ethoxylated tallow amines and oleic acid amide were compared using two ionization methods, positive-ion electrospray ionization (ESI) and AP-MALDI, using a LTQ Orbitrap mass spectrometer. Pure additives were characterized from solvent solutions, as well as from synthetic and mineral base oil mixtures. Detected ions of pure additive samples consisted mainly of [M + H]+, but also alkaLi metal adducts [M + Na]+ and [M + K]+ could be seen. Characterizations of blends of both friction modifiers from the base oil mixtures were carried out as well and showed significant inten- sities for several additive peaks. Thus, this work shows a method to directly analyze friction modifier additives used in the automotive industry from an oil blend via the use of AP-MALDI without any further separation steps. The method presented will further simplify the acquisition of data on lubricant composition and additives. Furthermore, it allows the perspective of analyzing additive reaction products directly from formulated oil blends.

Molecular interferometer to decode attosecond electron-nuclear dynamics.

PubMed

Palacios, Alicia; González-Castrillo, Alberto; Martín, Fernando

2014-03-18

Understanding the coupled electronic and nuclear dynamics in molecules by using pump-probe schemes requires not only the use of short enough laser pulses but also wavelengths and intensities that do not modify the intrinsic behavior of the system. In this respect, extreme UV pulses of few-femtosecond and attosecond durations have been recognized as the ideal tool because their short wavelengths ensure a negligible distortion of the molecular potential. In this work, we propose the use of two twin extreme UV pulses to create a molecular interferometer from direct and sequential two-photon ionization processes that leave the molecule in the same final state. We theoretically demonstrate that such a scheme allows for a complete identification of both electronic and nuclear phases in the wave packet generated by the pump pulse. We also show that although total ionization yields reveal entangled electronic and nuclear dynamics in the bound states, doubly differential yields (differential in both electronic and nuclear energies) exhibit in addition the dynamics of autoionization, i.e., of electron correlation in the ionization continuum. Visualization of such dynamics is possible by varying the time delay between the pump and the probe pulses.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fang, Li; Xiong, Hui; Kukk, Edwin

Molecular dynamics is of fundamental interest in natural science research. The capability of investigating molecular dynamics is one of the various motivations for ultrafast optics. Here, we present our investigation of photoionization and nuclear dynamics in methyl iodine (CH 3I) molecule with an X-ray pump X-ray probe scheme. The pump–probe experiment was realized with a two-mirror X-ray split and delay apparatus. Time-of-flight mass spectra at various pump–probe delay times were recorded to obtain the time profile for the creation of high charge states via sequential ionization and for molecular dissociation. We observed high charge states of atomic iodine up tomore » 29+, and visualized the evolution of creating these high atomic ion charge states, including their population suppression and enhancement as the arrival time of the second X-ray pulse was varied. We also show the evolution of the kinetics of the high charge states upon the timing of their creation during the ionization-dissociation coupled dynamics. We demonstrate the implementation of X-ray pump–probe methodology for investigating X-ray induced molecular dynamics with femtosecond temporal resolution. The results indicate the footprints of ionization that lead to high charge states, probing the long-range potential curves of the high charge states.« less

X-ray Pump–Probe Investigation of Charge and Dissociation Dynamics in Methyl Iodine Molecule

DOE PAGES

Fang, Li; Xiong, Hui; Kukk, Edwin; ...

2017-05-19

Molecular dynamics is of fundamental interest in natural science research. The capability of investigating molecular dynamics is one of the various motivations for ultrafast optics. Here, we present our investigation of photoionization and nuclear dynamics in methyl iodine (CH 3I) molecule with an X-ray pump X-ray probe scheme. The pump–probe experiment was realized with a two-mirror X-ray split and delay apparatus. Time-of-flight mass spectra at various pump–probe delay times were recorded to obtain the time profile for the creation of high charge states via sequential ionization and for molecular dissociation. We observed high charge states of atomic iodine up tomore » 29+, and visualized the evolution of creating these high atomic ion charge states, including their population suppression and enhancement as the arrival time of the second X-ray pulse was varied. We also show the evolution of the kinetics of the high charge states upon the timing of their creation during the ionization-dissociation coupled dynamics. We demonstrate the implementation of X-ray pump–probe methodology for investigating X-ray induced molecular dynamics with femtosecond temporal resolution. The results indicate the footprints of ionization that lead to high charge states, probing the long-range potential curves of the high charge states.« less

Global modeling of storm-time thermospheric dynamics and electrodynamics

NASA Astrophysics Data System (ADS)

Fuller-Rowell, T. J.; Richmond, A. D.; Maruyama, N.

Understanding the neutral dynamic and electrodynamic response of the upper atmosphere to geomagnetic storms, and quantifying the balance between prompt penetration and disturbance dynamo effects, are two of the significant challenges facing us today. This paper reviews our understanding of the dynamical and electrodynamic response of the upper atmosphere to storms from a modeling perspective. After injection of momentum and energy at high latitude during a geomagnetic storm, the neutral winds begin to respond almost immediately. The high-latitude wind system evolves quickly by the action of ion drag and the injection of kinetic energy; however, Joule dissipation provides the bulk of the energy source to change the dynamics and electrodynamics globally. Impulsive energy injection at high latitudes drives large-scale gravity waves that propagate globally. The waves transmit pressure gradients initiating a change in the global circulation. Numerical simulations of the coupled thermosphere, ionosphere, plasmasphere, and electrodynamic response to storms indicate that although the wind and waves are dynamic, with significant apparent "sloshing" between the hemispheres, the net effect is for an increased equatorward wind. The dynamic changes during a storm provide the conduit for many of the physical processes that ensue in the upper atmosphere. For instance, the increased meridional winds at mid latitudes push plasma parallel to the magnetic field to regions of different composition. The global circulation carries molecular rich air from the lower thermosphere upward and equatorward, changing the ratio of atomic and molecular neutral species, and changing loss rates for the ionosphere. The storm wind system also drives the disturbance dynamo, which through plasma transport modifies the strength and location of the equatorial ionization anomaly peaks. On a global scale, the increased equatorward meridional winds, and the generation of zonal winds at mid latitudes via the Coriolis effects, produce a current system opposing the normal quiet-time Sq current system. At the equator, the storm-time zonal electric fields reduce or reverse the normal upward and downward plasma drift on the dayside and nightside, respectively. In the numerical simulations, on the dayside, the disturbance dynamo appears fairly uniform, whereas at night a stronger local time dependence is apparent with increased upward drift between midnight and dawn. The simulations also indicate the possibility for a rapid dynamo response at the equator, within 2 h of storm onset, before the arrival of the large-scale gravity waves. All these wind-driven processes can result in dramatic ionospheric changes during storms. The disturbance dynamo can combine and interact with the prompt penetration of magnetospheric electric fields to the equator.

Changes in the Martian atmosphere induced by auroral electron precipitation

NASA Astrophysics Data System (ADS)

Shematovich, V. I.; Bisikalo, D. V.; Gérard, J.-C.; Hubert, B.

2017-09-01

Typical auroral events in the Martian atmosphere, such as discrete and diffuse auroral emissions detected by UV spectrometers onboard ESA Mars Express and NASA MAVEN, are investigated. Auroral electron kinetic energy distribution functions and energy spectra of the upward and downward electron fluxes are obtained by electron transport calculations using the kinetic Monte Carlo model. These characteristics of auroral electron fluxes make it possible to calculate both the precipitation-induced changes in the atmosphere and the observed manifestations of auroral events on Mars. In particular, intensities of discrete and diffuse auroral emissions in the UV and visible wavelength ranges (Soret et al., 2016; Bisikalo et al., 2017; Gérard et al., 2017). For these conditions of auroral events, the analysis is carried out, and the contribution of the fluxes of precipitating electrons to the heating and ionization of the Martian atmosphere is estimated. Numerical calculations show that in the case of discrete auroral events the effect of the residual crustal magnetic field leads to a significant increase in the upward fluxes of electrons, which causes a decrease in the rates of heating and ionization of the atmospheric gas in comparison with the calculations without taking into account the residual magnetic field. It is shown that all the above-mentioned impact factors of auroral electron precipitation processes should be taken into account both in the photochemical models of the Martian atmosphere and in the interpretation of observations of the chemical composition and its variations using the ACS instrument onboard ExoMars.

Analytical instruments, ionization sources, and ionization methods

DOEpatents

Atkinson, David A.; Mottishaw, Paul

2006-04-11

Methods and apparatus for simultaneous vaporization and ionization of a sample in a spectrometer prior to introducing the sample into the drift tube of the analyzer are disclosed. The apparatus includes a vaporization/ionization source having an electrically conductive conduit configured to receive sample particulate which is conveyed to a discharge end of the conduit. Positioned proximate to the discharge end of the conduit is an electrically conductive reference device. The conduit and the reference device act as electrodes and have an electrical potential maintained between them sufficient to cause a corona effect, which will cause at least partial simultaneous ionization and vaporization of the sample particulate. The electrical potential can be maintained to establish a continuous corona, or can be held slightly below the breakdown potential such that arrival of particulate at the point of proximity of the electrodes disrupts the potential, causing arcing and the corona effect. The electrical potential can also be varied to cause periodic arcing between the electrodes such that particulate passing through the arc is simultaneously vaporized and ionized. The invention further includes a spectrometer containing the source. The invention is particularly useful for ion mobility spectrometers and atmospheric pressure ionization mass spectrometers.

Rapid screening of basic colorants in processed vegetables through mass spectrometry using an interchangeable thermal desorption electrospray ionization source.

PubMed

Chao, Yu-Ying; Chen, Yen-Ling; Lin, Hong-Yi; Huang, Yeou-Lih

2018-06-20

Thermal desorption electrospray ionization/mass spectrometry (TD-ESI-MS) employing a quickly interchangeable ionization source is a relatively new ambient ionization mass spectrometric technique that has had, to date, only a limited number of applications related to food safety control. With reallocation of resources, this direct-analysis technique has had wider use in food analysis when operated in dual-working mode (pretreatment-free qualitative screening and conventional quantitative confirmation) after switching to an ambient ionization source from a traditional atmospheric pressure ionization source. Herein, we describe the benefits and challenges associated with the use of a TD-ESI source to detect adulterants in processed vegetables (PVs), as a proof-of-concept for the detection of basic colorants. While TD-ESI can offer direct qualitative screening analyses for PVs with detection capabilities lower than those provided with liquid chromatography/UV detection within 30 s, the use of TD-ESI for semi-quantification is applicable only for homogeneous food matrices. Copyright © 2018 Elsevier B.V. All rights reserved.

Modelling of plasma processes in cometary and planetary atmospheres

NASA Astrophysics Data System (ADS)

Campbell, L.; Brunger, M. J.

2013-02-01

Electrons from the Sun, often accelerated by magnetospheric processes, produce low-density plasmas in the upper atmospheres of planets and their satellites. The secondary electrons can produce further ionization, dissociation and excitation, leading to enhancement of chemical reactions and light emission. Similar processes are driven by photoelectrons produced by sunlight in upper atmospheres during daytime. Sunlight and solar electrons drive the same processes in the atmospheres of comets. Thus for both understanding of planetary atmospheres and in predicting emissions for comparison with remote observations it is necessary to simulate the processes that produce upper atmosphere plasmas. In this review, we describe relevant models and their applications and address the importance of electron-impact excitation cross sections, towards gaining a quantitative understanding of the phenomena in question.

Atmospheric Fluorescence Yield

NASA Technical Reports Server (NTRS)

Adams, James H., Jr.; Christl, M. J.; Fountain, W. F.; Gregory, J. C.; Martens, K.; Sokolsky, P.; Whitaker, Ann F. (Technical Monitor)

2001-01-01

Several existing and planned experiments estimate the energies of ultra-high energy cosmic rays from air showers using the atmospheric fluorescence from these showers. Accurate knowledge of the conversion from atmospheric fluorescence to energy loss by ionizing particles in the atmosphere is key to this technique. In this paper we discuss a small balloon-borne instrument to make the first in situ measurements versus altitude of the atmospheric fluorescence yield. The instrument can also be used in the lab to investigate the dependence of the fluorescence yield in air on temperature, pressure and the concentrations of other gases that present in the atmosphere. The results can be used to explore environmental effects on and improve the accuracy of cosmic ray energy measurements for existing ground-based experiments and future space-based experiments.

Dynamics of the CMZ - Giant Magnetic Loops Connection in the Galactic Center

NASA Astrophysics Data System (ADS)

Langer, William

2012-10-01

Understanding the mass transfer and dynamics among the Galactic Center, the disk, and the halo of the Milky Way is fundamental to the study of the evolution of galaxies and star formation. Several giant molecular loops (GML), detected in CO maps of the Galactic Center, are likely the result of the magnetic Parker instability. We have new evidence of a possible dynamical connection between these loops and the Central Molecular Zone (CMZ) from a sparse [CII] sampling from our Herschel Open Time Key Project GOT C+. The CMZ-GML region is dynamically active and is likely to have a significant ionized component. However, we have no information on the distribution and dynamics of the ionized gas. The fine-structure lines of [NII] are key probes of the warm ionized medium (WIM) and along with the [CII] can isolate the different ionization components. We have a Herschel OT2 Priority 1 program to map the GML and the CMZ-GML connection in [CII] in more detail. However, we did not propose needed [NII] observations due to an incomplete analysis of our limited GOT C+ data at the time. Here we propose to observe with the SOFIA/GREAT instrument, [NII] in the CMZ-GML interface region using the L1b band, and serendipitously CO (16-15) using band L2. With this data, combined with our Herschel HIFI [CII], Mopra 12CO (1-0) and 13CO (1-0), and HI, we will characterize these important ISM components and their motions in these Galactic Center features. These observations of the nearest such regions of galactic center activity, also have bearing on the dynamics of other galactic nuclei.

Under-the-barrier dynamics in laser-induced relativistic tunneling.

PubMed

Klaiber, Michael; Yakaboylu, Enderalp; Bauke, Heiko; Hatsagortsyan, Karen Z; Keitel, Christoph H

2013-04-12

The tunneling dynamics in relativistic strong-field ionization is investigated with the aim to develop an intuitive picture for the relativistic tunneling regime. We demonstrate that the tunneling picture applies also in the relativistic regime by introducing position dependent energy levels. The quantum dynamics in the classically forbidden region features two time scales, the typical time that characterizes the probability density's decay of the ionizing electron under the barrier (Keldysh time) and the time interval which the electron spends inside the barrier (Eisenbud-Wigner-Smith tunneling time). In the relativistic regime, an electron momentum shift as well as a spatial shift along the laser propagation direction arise during the under-the-barrier motion which are caused by the laser magnetic field induced Lorentz force. The momentum shift is proportional to the Keldysh time, while the wave-packet's spatial drift is proportional to the Eisenbud-Wigner-Smith time. The signature of the momentum shift is shown to be present in the ionization spectrum at the detector and, therefore, observable experimentally. In contrast, the signature of the Eisenbud-Wigner-Smith time delay disappears at far distances for pure quasistatic tunneling dynamics.

Simultaneous ESI-APCI+ ionization and fragmentation pathways for nine benzodiazepines and zolpidem using single quadrupole LC-MS.

PubMed

Galaon, Toma; Vacaresteanu, Catalina; Anghel, Dan-Florin; David, Victor

2014-05-01

Nine important 1,4-benzodiazepines and zolpidem were characterized by liquid chromatography-mass spectrometry using a multimode ionization source able to generate ions using both electrospray ionization (ESI) and atmospheric pressure chemical ionization (APCI), and a single quadrupole mass analyzer. An optimum chromatographic separation was applied for all target compounds in less than 8 minutes using a Zorbax Eclipse Plus column (100 × 4.6 mm, 3.5 µm) kept at 35°C and a 0.3% HCOOH/ACN/IPA (61:34:5) mobile phase pumped at 1 ml/min. Optimization of LC-MS method generated low limit of quantitation (LOQ) values situated in the range 0.3-20.5 ng/ml. Comparison between differences in method sensitivity, under specified chromatographic conditions, when using ESI-only, APCI-only, and simultaneous ESI-APCI ionization with such a multimode source was discussed. Mixed ESI-APCI(+) mode proved to be the most sensitive ionization generating an average 35% detector response increase compared to ESI-only ionization and 350% detector response increase with respect to APCI-only ionization. Characterization of the nine benzodiazepines and zolpidem concerning their MS fragmentation pathway following 'in-source' collision-induced dissociation is discussed in detail and some general trends regarding these fragmentations are set. Copyright © 2013 John Wiley & Sons, Ltd.

The Metal Oxide Space Clouds (MOSC) Experiment: High Frequency (HF) Signatures and Interactions with the Ambient Ionosphere

NASA Astrophysics Data System (ADS)

Groves, K. M.; Caton, R. G.; Pedersen, T. R.; Parris, R. T.; Su, Y.; Cannon, P. S.; Jackson-booth, N. K.; Angling, M. J.; Retterer, J. M.

2013-12-01

With support from the NASA sounding rocket team, AFRL performed two separate 5 kg releases of samarium metal vapor in the lower F-region near Kwajalein Atoll in May 2013. A fraction of the samarium subsequently ionized forming a plasma cloud that persisted for tens of minutes to hours in the post-sunset period. Numerous sensors were used to characterize the clouds including the ALTAIR incoherent scatter radar, multiple GPS and optical instruments, satellite radio beacons, and a dedicated network of high frequency (HF) radio links. The primary objectives of the experiments were to understand the dynamics, evolution and chemistry of Sm atoms in the earth's upper atmosphere. Sm is predicted to both photo-ionize and chemi-ionize through charge exchange with neutral oxygen (O). Ionization rates and loss reactions are not well known. A secondary objective was to understand the interaction of an artificial plasma cloud with the low latitude ionosphere during the pre-reversal enhancement period leading up to the post-sunset development of large-scale Rayleigh-Taylor instability. It was initially hoped that the introduction of the artificial plasma might be sufficient to quench the development of the instability by maintaining high conductivity within the affected flux tubes. Modeling results showed that this result was unlikely due to the relatively small amount of material being released. However, it appeared possible that the presence of SmO+ near the bottomside of the F-region might be capable of reducing the formation of short-scale irregularities within the larger Rayleigh-Taylor 'bubbles'. Indeed, preliminary results indicate that the artificial layers, positioned at 170 and 180 km respectively, did interact with the overlying F region and in at least one case, cause a decrease in the short-scale component of the natural irregularity spectrum. The results suggest that it may be possible to mitigate the formation of low-latitude irregularities responsible for radio wave scintillation with a MOSC-based approach.

Atmospheric pressure plasma accelerates tail regeneration in tadpoles Xenopus laevis

NASA Astrophysics Data System (ADS)

Rivie, A.; Martus, K.; Menon, J.

2017-08-01

Atmospheric pressure plasma is a partially ionized gas composed of neutral and charged particles, including electrons and ions, as well as reactive oxygen species (ROS). Recently, it is utilized as possible therapy in oncology, sterilization, skin diseases, wound healing and tissue regeneration. In this study we focused on effect of plasma exposure on tail regeneration of tadpoles, Xenopus leavis with special emphasis on role of ROS, antioxidant defenses and morphological features of the regenerate. When amputated region of the tail was exposed to the helium plasma it resulted in a faster rate of growth, elevated ROS and increase in antioxidant enzymes in the regenerate compared to that of untreated control. An increase in nitric oxide (free radical) as well as activity of nitric oxide synthase(s) were observed once the cells of the regeneration blastema - a mass of proliferating cells are ready for differentiation. Microscopically the cells of the regenerate of plasma treated tadpoles show altered morphology and characteristics of cellular hypoxia and oxidative stress. We summarize that plasma exposure accelerates the dynamics of wound healing and tail regeneration through its effects on cell proliferation and differentiation as well as angiogenesis mediated through ROS signaling.

[Gas chromatography with a Pulsed discharge helium ionization detector for measurement of molecular hydrogen(H2) in the atmosphere].

PubMed

Luan, Tian; Fang, Shuang-xi; Zhou, Ling-xi; Wang, Hong-yang; Zhang, Gen

2015-01-01

A high precision GC system with a pulsed discharge helium ionization detector was set up based on the commercial Agilent 7890A gas chromatography. The gas is identified by retention time and the concentration is calculated through the peak height. Detection limit of the system is about 1 x 10(-9) (mole fraction, the same as below). The standard deviation of 140 continuous injections with a standard cylinder( concentration is roughly 600 x 10(-9)) is better than 0.3 x 10(-9). Between 409.30 x 10(-9) and 867.74 x 10(-9) molecular hydrogen mole fractions and peak height have good linear response. By using two standards to quantify the air sample, the precision meets the background molecular hydrogen compatibility goal within the World Meteorological Organization/Global Atmosphere Watch (WMO/GAW) program. Atmospheric molecular hydrogen concentration at Guangzhou urban area was preliminarily measured by this method from January to November 2013. The results show that the atmospheric molecular hydrogen mole fraction varies from 450 x 10(-9) to 700 x 10(-9) during the observation period, with the lowest value at 14:00 (Beijing time, the same as below) and the peak value at 20:00. The seasonal variation of atmospheric hydrogen at Guangzhou area was similar with that of the same latitude stations in northern hemisphere.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

PubMed Central

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; Fang, Yigang; Kostko, Oleg

2017-01-01

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion–molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2)n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion–molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM. PMID:28484019

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

PubMed

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

2017-05-23

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE PAGES

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; ...

2017-05-08

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Ion Densities in the Nightside Ionosphere of Mars: Effects of Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Girazian, Z.; Mahaffy, P.; Lillis, R. J.; Benna, M.; Elrod, M.; Fowler, C. M.; Mitchell, D. L.

2017-11-01

We use observations from the Mars Atmosphere and Volatile EvolutioN (MAVEN) mission to show how superthermal electron fluxes and crustal magnetic fields affect ion densities in the nightside ionosphere of Mars. We find that due to electron impact ionization, high electron fluxes significantly increase the CO2+, O+, and O2+ densities below 200 km but only modestly increase the NO+ density. High electron fluxes also produce distinct peaks in the CO2+, O+, and O2+ altitude profiles. We also find that superthermal electron fluxes are smaller near strong crustal magnetic fields. Consequently, nightside ion densities are also smaller near strong crustal fields because they decay without being replenished by electron impact ionization. Furthermore, the NO+/O2+ ratio is enhanced near strong crustal fields because, in the absence of electron impact ionization, O2+ is converted into NO+ and not replenished. Our results show that electron impact ionization is a significant source of CO2+, O+, and O2+ in the nightside ionosphere of Mars.

Application of liquid chromatography-electrospray ionization mass spectrometry for study of steroid-converting enzymes.

PubMed

Miksík, Ivan; Mikulíková, Katerina; Pácha, Jirí; Kucka, Marek; Deyl, Zdenek

2004-02-05

A high-performance liquid chromatography-atmospheric pressure ionization-electrospray ionization mass spectrometry (HPLC-API-ESI-MS) method was developed for the analysis of steroids in a study of steroid-converting enzymes. Separations ware done on a Zorbax Eclipse XDB-C18 column (eluted with a linear methanol-water-acetic acid gradient) and identification of the steroids involved was done by API-ESI-MS using positive ion mode and extracted ion analysis. The applicability of the present method for studying steroid metabolism was proven in assaying two steroid-converting enzymes (20beta-hydroxysteroid dehydrogenase and 11beta-hydroxysteroid dehydrogenase) in various biological samples (rat and chicken intestine, chicken oviduct).

Review of chemical-kinetic problems of future NASA missions. I - Earth entries

NASA Technical Reports Server (NTRS)

Park, Chul

1993-01-01

A number of chemical-kinetic problems related to phenomena occurring behind a shock wave surrounding an object flying in the earth atmosphere are discussed, including the nonequilibrium thermochemical relaxation phenomena occurring behind a shock wave surrounding the flying object, problems related to aerobraking maneuver, the radiation phenomena for shock velocities of up to 12 km/sec, and the determination of rate coefficients for ionization reactions and associated electron-impact ionization reactions. Results of experiments are presented in form of graphs and tables, giving data on the reaction rate coefficients for air, the ionization distances, thermodynamic properties behind a shock wave, radiative heat flux calculations, Damkoehler numbers for the ablation-product layer, together with conclusions.

Lithium atoms on helium nanodroplets: Rydberg series and ionization dynamics

NASA Astrophysics Data System (ADS)

Lackner, Florian; Krois, Günter; Ernst, Wolfgang E.

2017-11-01

The electronic excitation spectrum of lithium atoms residing on the surface of helium nanodroplets is presented and analyzed employing a Rydberg-Ritz approach. Utilizing resonant two-photon ionization spectroscopy, two different Rydberg series have been identified: one assigned to the nS(Σ) series and the other with predominantly nP(Π) character. For high Rydberg states, which have been resolved up to n = 13, the surrounding helium effectively screens the valence electron from the Li ion core, as indicated by the apparent red-shift of Li transitions and lowered quantum defects on the droplet with respect to their free atom counterparts. For low n states, the screening effect is weakened and the prevailing repulsive interaction gives rise to strongly broadened and blue-shifted transitions. The red-shifts originate from the polarization of nearby He atoms by the positive Li ion core. As a consequence of this effect, the ionization threshold is lowered by 116 ± 10 cm-1 for Li on helium droplets with a radius of about 40 Å. Upon single-photon ionization, heavy complexes corresponding to Li ions attached to intact helium droplets are detected. We conclude that ionization close to the on-droplet ionization threshold triggers a dynamic process in which the Li ion core undergoes a transition from a surface site into the droplet.

A New Method Using Single-Particle Mass Spectrometry Data to Distinguish Mineral Dust and Biological Aerosols

NASA Astrophysics Data System (ADS)

Al-Mashat, H.; Kristensen, L.; Sultana, C. M.; Prather, K. A.

2016-12-01

The ability to distinguish types of particles present within a cloud is important for determining accurate inputs to climate models. The chemical composition of particles within cloud liquid droplets and ice crystals can have a significant impact on the timing, location, and amount of precipitation that falls. Precipitation efficiency is increased by the presence of ice crystals in clouds, and both mineral dust and biological aerosols have been shown to be effective ice nucleating particles (INPs) in the atmosphere. A current challenge in aerosol science is distinguishing mineral dust and biological material in the analysis of real-time, ambient, single-particle mass spectral data. Single-particle mass spectrometers are capable of measuring the size-resolved chemical composition of individual atmospheric particles. However, there is no consistent analytical method for distinguishing dust and biological aerosols. Sampling and characterization of control samples (i.e. of known identity) of mineral dust and bacteria were performed by the Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) as part of the Fifth Ice Nucleation (FIN01) Workshop at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) facility in Karlsruhe, Germany. Using data collected by the ATOFMS of control samples, a new metric has been developed to classify single particles as dust or biological independent of spectral cluster analysis. This method, involving the use of a ratio of mass spectral peak areas for organic nitrogen and silicates, is easily reproducible and does not rely on extensive knowledge of particle chemistry or the ionization characteristics of mass spectrometers. This represents a step toward rapidly distinguishing particle types responsible for ice nucleation activity during real-time sampling in clouds. The ability to distinguish types of particles present within a cloud is important for determining accurate inputs to climate models. The chemical composition of particles within cloud liquid droplets and ice crystals can have a significant impact on the timing, location, and amount of precipitation that falls. Precipitation efficiency is increased by the presence of ice crystals in clouds, and both mineral dust and biological aerosols have been shown to be effective ice nucleating particles (INPs) in the atmosphere. A current challenge in aerosol science is distinguishing mineral dust and biological material in the analysis of real-time, ambient, single-particle mass spectral data. Single-particle mass spectrometers are capable of measuring the size-resolved chemical composition of individual atmospheric particles. However, there is no consistent analytical method for distinguishing dust and biological aerosols. Sampling and characterization of control samples (i.e. of known identity) of mineral dust and bacteria were performed by the Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) as part of the Fifth Ice Nucleation (FIN01) Workshop at the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) facility in Karlsruhe, Germany. Using data collected by the ATOFMS of control samples, a new metric has been developed to classify single particles as dust or biological independent of spectral cluster analysis. This method, involving the use of a ratio of mass spectral peak areas for organic nitrogen and silicates, is easily reproducible and does not rely on extensive knowledge of particle chemistry or the ionization characteristics of mass spectrometers. This represents a step toward rapidly distinguishing particle types responsible for ice nucleation activity during real-time sampling in clouds.

Laser-Induced Acoustic Desorption Atmospheric Pressure Photoionization via VUV-Generating Microplasmas.

PubMed

Benham, Kevin; Hodyss, Robert; Fernández, Facundo M; Orlando, Thomas M

2016-11-01

We demonstrate the first application of laser-induced acoustic desorption (LIAD) and atmospheric pressure photoionization (APPI) as a mass spectrometric method for detecting low-polarity organics. This was accomplished using a Lyman-α (10.2 eV) photon generating microhollow cathode discharge (MHCD) microplasma photon source in conjunction with the addition of a gas-phase molecular dopant. This combination provided a soft desorption and a relatively soft ionization technique. Selected compounds analyzed include α-tocopherol, perylene, cholesterol, phenanthrene, phylloquinone, and squalene. Detectable surface concentrations as low as a few pmol per spot sampled were achievable using test molecules. The combination of LIAD and APPI provided a soft desorption and ionization technique that can allow detection of labile, low-polarity, structurally complex molecules over a wide mass range with minimal fragmentation. Graphical Abstract ᅟ.

Solid-Phase Microextraction Coupled to Capillary Atmospheric Pressure Photoionization-Mass Spectrometry for Direct Analysis of Polar and Nonpolar Compounds.

PubMed

Mirabelli, Mario F; Zenobi, Renato

2018-04-17

A novel capillary ionization source based on atmospheric pressure photoionization (cAPPI) was developed and used for the direct interfacing between solid-phase microextraction (SPME) and mass spectrometry (MS). The efficiency of the source was evaluated for direct and dopant-assisted photoionization, analyzing both polar (e.g., triazines and organophosphorus pesticides) and nonpolar (polycyclic aromatic hydrocarbons, PAHs) compounds. The results show that the range of compound polarity, which can be addressed by direct SPME-MS can be substantially extended by using cAPPI, compared to other sensitive techniques like direct analysis in real time (DART) and dielectric barrier discharge ionization (DBDI). The new source delivers a very high sensitivity, down to sub parts-per-trillion (ppt), making it a viable alternative when compared to previously reported and less comprehensive direct approaches.

Degradation of the Neonicotinoid Pesticides in the Atmospheric Pressure Ionization Source

NASA Astrophysics Data System (ADS)

Chai, Yunfeng; Chen, Hongping; Liu, Xin; Lu, Chengyin

2018-02-01

During the analysis of neonicotinoid pesticide standards (thiamethoxam, clothianidin, imidacloprid, acetamiprid, and thiacloprid) by mass spectrometry, the degradation of these pesticides (M-C=N-R is degraded into M-C=O, M is the skeleton moiety, and R is NO2 or CN) was observed in the atmospheric pressure ionization interfaces (ESI and APCI). In APCI, the degradation of all the five neonicotinoid pesticides studied took place, and the primary mechanism was in-source ion/molecule reaction, in which a molecule of water (confirmed by use of H2 18O) attacked the carbon of the imine group accompanying with loss of NH2R (R=NO2, CN). For the nitroguanidine neonicotinoid pesticides (R=NO2, including thiamethoxam, clothianidin, and imidacloprid), higher auxiliary gas heater temperature also contributed to their degradation in APCI due to in-source pyrolysis. The degradation of the five neonicotinoid pesticides studied in ESI was not significant. In ESI, only the nitroguanidine neonicotinoid pesticides could generate the degradation products through in-source fragmentation mechanism. The degradation of cyanoamidine neonicotinoid pesticides (R=CN, including acetamiprid and thiacloprid) in ESI was not observed. The degradation of neonicotinoid pesticides in the ion source of mass spectrometer renders some adverse consequences, such as difficulty interpreting the full-scan mass spectrum, reducing the sensitivity and accuracy of quantitative analysis, and misleading whether these pesticides have degraded in the real samples. Therefore, a clear understanding of these unusual degradation reactions should facilitate the analysis of neonicotinoid pesticides by atmospheric pressure ionization mass spectrometry.

Energy deposition dynamics of femtosecond pulses in water

DOE Office of Scientific and Technical Information (OSTI.GOV)

Minardi, Stefano, E-mail: stefano@stefanominardi.eu; Pertsch, Thomas; Milián, Carles

2014-12-01

We exploit inverse Raman scattering and solvated electron absorption to perform a quantitative characterization of the energy loss and ionization dynamics in water with tightly focused near-infrared femtosecond pulses. A comparison between experimental data and numerical simulations suggests that the ionization energy of water is 8 eV, rather than the commonly used value of 6.5 eV. We also introduce an equation for the Raman gain valid for ultra-short pulses that validates our experimental procedure.

Measuring the effects of Coulomb repulsion via signal decay in an atmospheric pressure laser ionization ion mobility spectrometer.

PubMed

Ihlenborg, Marvin; Schuster, Ann-Kathrin; Grotemeyer, Juergen; Gunzer, Frank

2018-01-01

Using lasers in ion mobility spectrometry offers a lot of advantages compared to standard ionization sources. Especially, the ion yield can be drastically increased. It can, however, reach levels where the Coulomb repulsion leads to unwanted side effects. Here, we investigate how the Coulomb repulsion can be detected apart from the typical signal broadening by measuring effects created already in the reaction region and comparing them with corresponding finite element method simulations.

A Radical-Mediated Pathway for the Formation of [M + H](+) in Dielectric Barrier Discharge Ionization.

PubMed

Wolf, Jan-Christoph; Gyr, Luzia; Mirabelli, Mario F; Schaer, Martin; Siegenthaler, Peter; Zenobi, Renato

2016-09-01

Active capillary plasma ionization is a highly efficient ambient ionization method. Its general principle of ion formation is closely related to atmospheric pressure chemical ionization (APCI). The method is based on dielectric barrier discharge ionization (DBDI), and can be constructed in the form of a direct flow-through interface to a mass spectrometer. Protonated species ([M + H](+)) are predominantly formed, although in some cases radical cations are also observed. We investigated the underlying ionization mechanisms and reaction pathways for the formation of protonated analyte ([M + H](+)). We found that ionization occurs in the presence and in the absence of water vapor. Therefore, the mechanism cannot exclusively rely on hydronium clusters, as generally accepted for APCI. Based on isotope labeling experiments, protons were shown to originate from various solvents (other than water) and, to a minor extent, from gaseous impurities and/or self-protonation. By using CO2 instead of air or N2 as plasma gas, additional species like [M + OH](+) and [M - H](+) were observed. These gas-phase reaction products of CO2 with the analyte (tertiary amines) indicate the presence of a radical-mediated ionization pathway, which proceeds by direct reaction of the ionized plasma gas with the analyte. The proposed reaction pathway is supported with density functional theory (DFT) calculations. These findings add a new ionization pathway leading to the protonated species to those currently known for APCI. Graphical Abstract ᅟ.

Low-sample flow secondary electrospray ionization: improving vapor ionization efficiency.

PubMed

Vidal-de-Miguel, G; Macía, M; Pinacho, P; Blanco, J

2012-10-16

In secondary electrospray ionization (SESI) systems, gaseous analytes exposed to an elecrospray plume become ionized after charge is transferred from the charging electrosprayed particles to the sample species. Current SESI systems have shown a certain potential. However, their ionization efficiency is limited by space charge repulsion and by the high sample flows required to prevent vapor dilution. As a result, they have a poor conversion ratio of vapor into ions. We have developed and tested a new SESI configuration, termed low-flow SESI, that permits the reduction of the required sample flows. Although the ion to vapor concentration ratio is limited, the ionic flow to sample vapor flow ratio theoretically is not. The new ionizer is coupled to a planar differential mobility analyzer (DMA) and requires only 0.2 lpm of vapor sample flow to produce 3.5 lpm of ionic flow. The achieved ionization efficiency is 1/700 (one ion for every 700 molecules) for TNT and, thus, compared with previous SESI ionizers coupled with atmospheric pressure ionization-mass spectrometry (API-MS) (Mesonero, E.; Sillero, J. A.; Hernández, M.; Fernandez de la Mora, J. Philadelphia PA, 2009) has been improved by a large factor of at least 50-100 (our measurements indicate 70). The new ionizer coupled with the planar DMA and a triple quadrupole mass spectrometer (ABSciex API5000) requires only 20 fg (50 million molecules) to produce a discernible signal after mobility and MS(2) analysis.

Use of capillary gas chromatography with negative ion-chemical ionization mass spectrometry for the determination of perfluorocarbon tracers in the atmosphere.

PubMed

Cooke, K M; Simmonds TPG; Nickless, G; Makepeace, A P

2001-09-01

A sensitive and selective technique for the quantitative measurement of atmospheric perfluorocarbon trace species at the sub part per quadrillion (10(-15)) levels is presented. The method utilizes advances in adsorbent enrichment techniques coupled with benchtop capillary gas chromatography and negative ion-chemical ionization mass spectrometry. The development and enhancement of sampling technology for tracer experiments is described, and the results from background measurements and a preliminary field experiment are presented. The overall precision of the analytical method with respect to the preferred tracer for these atmospheric transport studies, perfluoromethylcyclohexane, was +/-1.7%. The background concentrations of perfluorodimethylcyclobutane, perfluoromethylcyclopentane, and perfluoromethylcyclohexane at a remote coastal location (Mace Head, Ireland, 53 degrees N, 10 degrees W) were found to be 2.5 (+/-0.4), 6.8 (+/-1.0), and 5.2 fL L(-1) (+/-1.3), respectively. Background concentrations within an urban conurbation (Bristol, U.K.) were slightly greater at 3.0 (+/-1.5), 8.1 (+/-1.8), and 6.3 fL L(-1) (+/-1.1), respectively.

Steps towards understanding deep atmospheric heating in flares

NASA Technical Reports Server (NTRS)

Mauas, Pablo J. D.; Machado, Marcos E.

1986-01-01

Different aspects of the heating of the deep solar atmosphere during flares, including temperature minimum enhancements and white light emission, are discussed. The proper treatment of H(-) radiative losses is discussed, and compared with previous studies, as well as a quantitative analysis of the ionizing effect of nonthermal particles and ultraviolet radiation. It is concluded that temperature minimum heating may be a natural consequence of the global radiation transport in flares. The implications of these results are discussed within the context of homogeneous and inhomogeneous models of the solar atmosphere.

Dynamic Reactive Ionization with Cluster Secondary Ion Mass Spectrometry

NASA Astrophysics Data System (ADS)

Tian, Hua; Wucher, Andreas; Winograd, Nicholas

2016-02-01

Gas cluster ion beams (GCIB) have been tuned to enhance secondary ion yields by doping small gas molecules such as CH4, CO2, and O2 into an Ar cluster projectile, Arn + ( n = 1000-10,000) to form a mixed cluster. The `tailored beam' has the potential to expand the application of secondary ion mass spectrometry for two- and three-dimensional molecular specific imaging. Here, we examine the possibility of further enhancing the ionization by doping HCl into the Ar cluster. Water deposited on the target surface facilitates the dissociation of HCl. This concerted effect, occurring only at the impact site of the cluster, arises since the HCl is chemically induced to ionize to H+ and Cl- , allowing improved protonation of neutral molecular species. This hypothesis is confirmed by depth profiling through a trehalose thin film exposed to D2O vapor, resulting in ~20-fold increase in protonated molecules. The results show that it is possible to dynamically maintain optimum ionization conditions during depth profiling by proper adjustment of the water vapor pressure. H-D exchange in the trehalose molecule M was monitored upon deposition of D2O on the target surface, leading to the observation of [Mn* + H]+ or [Mn* + D]+ ions, where n = 1-8 hydrogen atoms in the trehalose molecule M have been replaced by deuterium. In general, we discuss the role of surface chemistry and dynamic reactive ionization of organic molecules in increasing the secondary ion yield.

Generation of monoenergetic ion beams via ionization dynamics (Conference Presentation)

NASA Astrophysics Data System (ADS)

Lin, Chen; Kim, I. Jong; Yu, Jinqing; Choi, Il Woo; Ma, Wenjun; Yan, Xueqing; Nam, Chang Hee

2017-05-01

The research on ion acceleration driven by high intensity laser pulse has attracted significant interests in recent decades due to the developments of laser technology. The intensive study of energetic ion bunches is particularly stimulated by wide applications in nuclear fusion, medical treatment, warm dense matter production and high energy density physics. However, to implement such compact accelerators, challenges are still existing in terms of beam quality and stability, especially in applications that require higher energy and narrow bandwidth spectra ion beams. We report on the acceleration of quasi-mono-energetic ion beams via ionization dynamics in the interaction of an intense laser pulse with a solid target. Using ionization dynamics model in 2D particle-in-cell (PIC) simulations, we found that high charge state contamination ions can only be ionized in the central spot area where the intensity of sheath field surpasses their ionization threshold. These ions automatically form a microstructure target with a width of few micron scale, which is conducive to generate mono-energetic beams. In the experiment of ultraintense (< 10^21 W/cm^2) laser pulses irradiating ultrathin targets each attracted with a contamination layer of nm-thickness, high quality < 100 MeV mono-energetic ion bunches are generated. The peak energy of the self-generated micro-structured target ions with respect to different contamination layer thickness is also examined This is relatively newfound respect, which is confirmed by the consistence between experiment data and the simulation results.

A single-electron picture based on the multiconfiguration time-dependent Hartree-Fock method: application to the anisotropic ionization and subsequent high-harmonic generation of the CO molecule

NASA Astrophysics Data System (ADS)

Ohmura, S.; Kato, T.; Oyamada, T.; Koseki, S.; Ohmura, H.; Kono, H.

2018-02-01

The mechanisms of anisotropic near-IR tunnel ionization and high-order harmonic generation (HHG) in a CO molecule are theoretically investigated by using the multiconfiguration time-dependent Hartree-Fock (MCTDHF) method developed for the simulation of multielectron dynamics of molecules. The multielectron dynamics obtained by numerically solving the equations of motion (EOMs) in the MCTDHF method is converted to a single orbital picture in the natural orbital representation where the first-order reduced density matrix is diagonalized. The ionization through each natural orbital is examined and the process of HHG is classified into different optical paths designated by a combinations of initial, intermediate and final natural orbitals. The EOMs for natural spin-orbitals are also derived within the framework of the MCTDHF, which maintains the first-order reduced density matrix to be a diagonal one throughout the time propagation of a many-electron wave function. The orbital dependent, time-dependent effective potentials that govern the dynamics of respective time-dependent natural orbitals are deduced from the derived EOMs, of which the temporal variation can be used to interpret the motion of the electron density associated with each natural spin-orbital. The roles of the orbital shape, multiorbital ionization, linear Stark effect and multielectron interaction in the ionization and HHG of a CO molecule are revealed by the effective potentials obtained. When the laser electric field points to the nucleus O from C, tunnel ionization from the C atom side is enhanced; a hump structure originating from multielectron interaction is then formed on the top of the field-induced distorted barrier of the HOMO effective potential. This hump formation, responsible for the directional anisotropy of tunnel ionization, restrains the influence of the linear Stark effect on the energy shifts of bound states.

Dynamical orientation effects in atomic ionization by impact of protons and positrons

NASA Astrophysics Data System (ADS)

Fregenal, Daniel; Barrachina, Raúl; Bernardi, Guillermo; Suárez, Sergio; Fiol, Juan

2011-10-01

Recent results in ionization collisions with positrons and protons showed that just above the two-body threshold, for electron velocities close to the final projectile's velocity, the electron-projectile continuum dipole is narrowly oriented along the direction of motion of its centre-of-mass, with the negative charge pointing towards the residual target. Although a forward-backward asymmetry in the vicinity of the two-body threshold has been studied many year ago in ion impact ionization collisions, that was by far a much milder effect that left no fingerprint on the cusp position. Our results show that the phenomena is present for ionization by impact of both protons and positrons. In this communication, through measurements on H+ + He and calculations we analyze in detail this effect that can be linked to a dynamical alignment of the two-body subsystem in the continuum. Recent results in ionization collisions with positrons and protons showed that just above the two-body threshold, for electron velocities close to the final projectile's velocity, the electron-projectile continuum dipole is narrowly oriented along the direction of motion of its centre-of-mass, with the negative charge pointing towards the residual target. Although a forward-backward asymmetry in the vicinity of the two-body threshold has been studied many year ago in ion impact ionization collisions, that was by far a much milder effect that left no fingerprint on the cusp position. Our results show that the phenomena is present for ionization by impact of both protons and positrons. In this communication, through measurements on H+ + He and calculations we analyze in detail this effect that can be linked to a dynamical alignment of the two-body subsystem in the continuum. This work was partially supported by the Consejo Nacional de Investigaciones Cientificas y Tecnicas, Universidad Nacional de Cuyo and Fundacion Balseiro.

Gravito-electrodynamics, Ehd and Their Applications To Natural Hazards and Laboratory Devices

NASA Astrophysics Data System (ADS)

Kikuchi, H.

For the past two decades, theory of dusty and dirty plasmas in space and in the labo - ratory has been developed on the basis of both unconventional gravito-electrody- nam ics and a new EHD (electrohydrodynamics) with novel concepts of electric re- connection and critical ionization velocity as well as modern concepts of self-organ- ization and chaos and has been applied to explanations of a variety of new dust-re- lated and meteorologyico-electric phenomena such as planetary (Saturn's and Jupi- ter's) dust layer or ring formation, terrestrial dust layer formation, terrestrial light - ning including winter thunderstorms, rocket and tower triggered lightning, planetary (Saturn's, Jupiter's, and Io's) lightning, nebular lightning, ball lightning, tornadic thunderstorms, whirlwinds, cloud-to-ionosphere discharges, pre-earthquake atmo- sphereic and ionospheric effects, and new laboratory devices such as electric undu - lators, a universal electric-cusp type plasma reactor for basic laboratory studies, sim- ulations of atmospheric phenomena and pollution control and gas cleaning, plasma processing and new material production for industrial applications, and new devices such as towards cancer treatment for biological and medical applications. Reference H. Kikuchi, Electrohydrodynamics in Dusty and Dirty plasmas, Kluwer Academic Publishers, Dordrecht/The Netherlands, 2001. For describing any plasmas, particle dynamics plays always fundamental and impor - tant roles in understanding all of plasma behaviors. A variety of descriptions in a magnetic field such as a guiding center approach have well been developed as a test-particle approach particularly for a base of MHD. This is still true for EHD or EMHD, but additional factors become significant due to the existence of space charges and electric fields for EHD or EMHD in dielectric or semiconducting fluids. In cosmic plasmas, the existence of double layers, electric and magnetic dipoles or quadru-poles often affects the particle motions drastically even if particles are uncharged, and can play a crucial role in planetary dust layer or ring formation. This is a new discov-ery and has been discussed in detail for the past several EGS meetings. In the presenc e of quadrupole-like charged cloud configurations which constitute electric cusps and mirrors, a neutral or uncharged particle can be accelerated in an electric cusp, reaching a maximum speed near a cusp boundary, if the environment is a tenuous gas whatever it may be neutral or ionized, and also can be reflected back at a mirror point. Otherwise, a dust in an electric cusp is capable for a source origin of plasma layer formation, gas discharges or lightnings due to additional effect of `criti-cal velocity' if the local electric fields around the dust produced by quadrupole-like charged clouds are sufficiently high beyond a gas-breakdown threshold. Then electric reconnection through the dust is followed by streamer or leader formation due to the critical ionization effect and consequent gas discharges or lightnings. One of major features of new electrodynamics, gravito-electrodynamics, and EHD is a new addition of two basic concepts of electric reconnection and critical ionization . First, one may recall that a distribution of scattered charged clouds is so ubiquitous in space and in the laboratory, even in our daily life, whatever they are of large-scale or small-scale, like thunderclouds in the atmosphere, charged clouds in interstellar space, charges on the belt of Van de Graff generator, and a system of miniature thunder-clouds produced by frictional electricity almost everywhere, typically on human hairs. All those cases are capable for electric reconnection. Whenever electric reconnection occurs through dusts in the atmosphere, it can be accompanied by a critical ioniza-tion flow . In this way, electric reconnection and critical ionization could be a signifi-cant cause of electrification and electric discharge and play important roles in a varie-ty of phenomena in meteorologico-electric, dusty and dirty plasma environments.

Trace determination of 13 haloacetamides in drinking water using liquid chromatography triple quadrupole mass spectrometry with atmospheric pressure chemical ionization.

PubMed

Chu, Wenhai; Gao, Naiyun; Yin, Daqiang; Krasner, Stuart W; Templeton, Michael R

2012-04-27

The haloacetamides (HAcAms) are disinfection by-products (DBPs) in drinking water which are currently receiving increased scientific attention due to their elevated toxicity relative to regulated disinfection by-products. A simultaneous determination method of 13 HAcAms, combining solid-phase extraction (SPE) enrichment, liquid chromatographic (LC) separation, and triple quadrupole mass spectrometry (tqMS) detection with atmospheric pressure chemical ionization (APCI) using selective reaction monitoring in positive mode, was developed to measure HAcAms, including chlorinated, brominated, and iodinated analogs. Ammonium chloride and Oasis HLB were selected as the dechlorinating reagent and polymeric SPE sorbent of HAcAm samples. The used tqMS apparatus showed higher sensitivity for the studied HAcAms in the APCI mode than electrospray ionization. 13 HAcAms were separated by LC in 9.0 min, and the detection limits ranged from 7.6 to 19.7 ng/L. The SPE-LC/tqMS method was successfully applied to quantify 13 HAcAms in drinking water samples for the first time, and first indentified tribromoacetamide and chloroiodoacetamide as DBPs in drinking water. Copyright © 2012 Elsevier B.V. All rights reserved.

Molecular dynamics simulation of Coulomb explosion, melting and shock wave creation in silicon after an ionization pulse

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhongyu; Shao, Lin, E-mail: lshao@tamu.edu; Chen, Di

Strong electronic stopping power of swift ions in a semiconducting or insulating substrate can lead to localized electron stripping. The subsequent repulsive interactions among charged target atoms can cause Coulomb explosion. Using molecular dynamics simulation, we simulate Coulomb explosion in silicon by introducing an ionization pulse lasting for different periods, and at different substrate temperatures. We find that the longer the pulse period, the larger the melting radius. The observation can be explained by a critical energy density model assuming that melting required thermal energy density is a constant value and the total thermal energy gained from Coulomb explosion ismore » linearly proportional to the ionization period. Our studies also show that melting radius is larger at higher substrate temperatures. The temperature effect is explained due to a longer structural relaxation above the melting temperature at original ionization boundary due to lower heat dissipation rates. Furthermore, simulations show the formation of shock waves, created due to the compression from the melting core.« less

Atmospheric pressure plasma jet with high-voltage power supply based on piezoelectric transformer.

PubMed

Babij, Michał; Kowalski, Zbigniew W; Nitsch, Karol; Silberring, Jerzy; Gotszalk, Teodor

2014-05-01

The dielectric barrier discharge plasma jet, an example of the nonthermal atmospheric pressure plasma jet (APPJ), generates low-temperature plasmas that are suitable for the atomization of volatile species and can also be served as an ionization source for ambient mass and ion mobility spectrometry. A new design of APPJ for mass spectrometry has been built in our group. In these plasma sources magnetic transformers (MTs) and inductors are typically used in power supplies but they present several drawbacks that are even more evident when dealing with high-voltage normally used in APPJs. To overcome these disadvantages, high frequency generators with the absence of MT are proposed in the literature. However, in the case of miniaturized APPJs these conventional power converters, built of ferromagnetic cores and inductors or by means of LC resonant tank circuits, are not so useful as piezoelectric transformer (PT) based power converters due to bulky components and small efficiency. We made and examined a novel atmospheric pressure plasma jet with PT supplier served as ionization source for ambient mass spectrometry, and especially mobile spectrometry where miniaturization, integration of components, and clean plasma are required. The objective of this paper is to describe the concept, design, and implementation of this miniaturized piezoelectric transformer-based atmospheric pressure plasma jet.

Atmospheric pressure plasma jet with high-voltage power supply based on piezoelectric transformer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babij, Michał; Kowalski, Zbigniew W., E-mail: zbigniew.w.kowalski@pwr.wroc.pl; Nitsch, Karol

The dielectric barrier discharge plasma jet, an example of the nonthermal atmospheric pressure plasma jet (APPJ), generates low-temperature plasmas that are suitable for the atomization of volatile species and can also be served as an ionization source for ambient mass and ion mobility spectrometry. A new design of APPJ for mass spectrometry has been built in our group. In these plasma sources magnetic transformers (MTs) and inductors are typically used in power supplies but they present several drawbacks that are even more evident when dealing with high-voltage normally used in APPJs. To overcome these disadvantages, high frequency generators with themore » absence of MT are proposed in the literature. However, in the case of miniaturized APPJs these conventional power converters, built of ferromagnetic cores and inductors or by means of LC resonant tank circuits, are not so useful as piezoelectric transformer (PT) based power converters due to bulky components and small efficiency. We made and examined a novel atmospheric pressure plasma jet with PT supplier served as ionization source for ambient mass spectrometry, and especially mobile spectrometry where miniaturization, integration of components, and clean plasma are required. The objective of this paper is to describe the concept, design, and implementation of this miniaturized piezoelectric transformer-based atmospheric pressure plasma jet.« less

Alternative food safety intervention technologies

USDA-ARS?s Scientific Manuscript database

Alternative nonthermal and thermal food safety interventions are gaining acceptance by the food processing industry and consumers. These technologies include high pressure processing, ultraviolet and pulsed light, ionizing radiation, pulsed and radiofrequency electric fields, cold atmospheric plasm...

In situ mass analysis of particles by surface ionization mass spectrometry

NASA Technical Reports Server (NTRS)

Lassiter, W. S.; Moen, A. L.

1974-01-01

A qualitative study of the application of surface ionization and mass spectrometry to the in situ detection and constituent analysis of atmospheric particles was conducted. The technique consists of mass analysis of ions formed as a result of impingement of a stream of particles on a hot filament where, it is presumed, surface ionization takes place. Laboratory air particles containing K, Ca, and possibly hydrocarbons were detected. Other known particles such as Al2O3, Pb(NO3)2, and Cr2O3 were analyzed by detecting the respective metal atoms making up the particles. In some cases, mass numbers indicative of compounds making up the particles were detected showing surface ionization of particles sometimes leads to chemical analysis as well as to elemental analysis. Individual particles were detected, and it was shown that the technique is sensitive to Al2O3 particles with a mass of a few nanograms.

From Core to Solar Wind: Studying the Space Environment of Planets

NASA Astrophysics Data System (ADS)

Bagenal, F.

2004-05-01

Space physics permeates studies of the planets - from the magnetic field generated in a planetary core, through the charged particle bombardment of surfaces, the heating, excitation and ionization of an atmosphere or corona, to the acceleration of ions and electrons trapped in a planet's magnetosphere. This presentation provides an introductory overview of the space environment of planetary objects - from giant planets to tiny comets. The talk highlights three cases that illustrate the range of issues and applications of planetary space physics. (1) How has the solar wind interaction with Mars' strong, patchy remnant magnetization affected the loss of water? (2) How does the activity of volcanoes on Io trigger dynamics of the vast magnetosphere of Jupiter? (3) How could measurements of particles and fields by the Galileo spacecraft as it flew past Ganymede and Europa tell us that former has a liquid iron core and the latter a layer of liquid water?

Vibrational-rotational temperature measurement of N2 in the lower thermosphere by the rocket experiment

NASA Astrophysics Data System (ADS)

Kurihara, J.; Oyama, K.; Suzuki, K.; Iwagami, N.

The vibrational temperature (Tv), the rotational temperature (Tr) and the density of atmospheric N2 between 100 - 150 km were measured in situ by a sounding rocket S310-30, over Kagoshima, Japan at 10:30 UT on February 6, 2002. The main purpose of this rocket experiment is to study the dynamics and the thermal energy budget in the lower thermosphere. N2 was ionized using an electron gun and the emission of the 1st negative bands of N2+ was measured by a sensitive spectrometer. Tv and Tr were determined by fitting the observed spectrum for the simulated spectrum, and the number density was deduced from the intensities of the spectrum. We will report preliminary results of our measurement and discuss the observed thermal structure that indicates the effect of tides and gravity waves.

High Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) for Mass Spectrometry-Based Proteomics

PubMed Central

Swearingen, Kristian E.; Moritz, Robert L.

2013-01-01

SUMMARY High field asymmetric waveform ion mobility spectrometry (FAIMS) is an atmospheric pressure ion mobility technique that separates gas-phase ions by their behavior in strong and weak electric fields. FAIMS is easily interfaced with electrospray ionization and has been implemented as an additional separation mode between liquid chromatography (LC) and mass spectrometry (MS) in proteomic studies. FAIMS separation is orthogonal to both LC and MS and is used as a means of on-line fractionation to improve detection of peptides in complex samples. FAIMS improves dynamic range and concomitantly the detection limits of ions by filtering out chemical noise. FAIMS can also be used to remove interfering ion species and to select peptide charge states optimal for identification by tandem MS. Here, we review recent developments in LC-FAIMS-MS and its application to MS-based proteomics. PMID:23194268

Real-time analysis of ambient organic aerosols using aerosol flowing atmospheric-pressure afterglow mass spectrometry (AeroFAPA-MS)

NASA Astrophysics Data System (ADS)

Brüggemann, Martin; Karu, Einar; Stelzer, Torsten; Hoffmann, Thorsten

2015-04-01

Organic aerosol accounts for a major fraction of atmospheric aerosols and has implications on the earth's climate and human health. However, due to the chemical complexity its measurement remains a major challenge for analytical instrumentation.1 Here, we present the development, characterization and application of a new soft ionization technique that allows mass spectrometric real-time detection of organic compounds in ambient aerosols. The aerosol flowing atmospheric-pressure afterglow (AeroFAPA) ion source utilizes a helium glow discharge plasma to produce excited helium species and primary reagent ions. Ionization of the analytes occurs in the afterglow region after thermal desorption and results mainly in intact molecular ions, facilitating the interpretation of the acquired mass spectra. In the past, similar approaches were used to detect pesticides, explosives or illicit drugs on a variety of surfaces.2,3 In contrast, the AeroFAPA source operates 'online' and allows the detection of organic compounds in aerosols without a prior precipitation or sampling step. To our knowledge, this is the first application of an atmospheric-pressure glow discharge ionization technique to ambient aerosol samples. We illustrate that changes in aerosol composition and concentration are detected on the time scale of seconds and in the ng-m-3 range. Additionally, the successful application of AeroFAPA-MS during a field study in a mixed forest region in Central Europe is presented. Several oxidation products of monoterpenes were clearly identified using the possibility to perform tandem MS experiments. The acquired data are in agreement with previous studies and demonstrate that AeroFAPA-MS is a suitable tool for organic aerosol analysis. Furthermore, these results reveal the potential of this technique to enable new insights into aerosol formation, growth and transformation in the atmosphere. References: 1) IPCC, 2013: Summary for Policymakers. In: Climate Change 2013: The Physical Science Basis. Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change [Stocker, T.F., D. Qin, G.-K. Plattner, M. Tignor, S.K. Allen, J. Boschung, A. Nauels, Y. Xia, V. Bex and P.M. Midgley (eds.)]. Cambridge University Press, Cambridge, United Kingdom and New York, NY, USA, in press. 2) Shelley, J. T.; Wiley, J. S.; Hieftje, G. M. Ultrasensitive Ambient Mass Spectrometric Analysis with a Pin-to-Capillary Flowing Atmospheric-Pressure Afterglow Source. Anal. Chem. 2011, 83(14), 5741-5748; DOI 10.1021/Ac201053q. 3) Albert, A.; Shelley, J.; Engelhard, C. Plasma-based ambient desorption/ionization mass spectrometry: state-of-the-art in qualitative and quantitative analysis. Anal Bioanal Chem 2014, 406(25), 6111-6127; DOI 10.1007/s00216-014-7989-z.

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography.

PubMed

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Liu, Peng; Chen, Zhangjin; Yang, Weifeng; Hu, Shilin; Lin, C D; Chen, Jing

2016-06-22

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. In addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. We showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules.

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography

PubMed Central

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; Liu, Peng; Chen, Zhangjin; Yang, Weifeng; Hu, Shilin; Lin, C. D.; Chen, Jing

2016-01-01

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. In addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. We showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules. PMID:27329071

Unraveling nonadiabatic ionization and Coulomb potential effect in strong-field photoelectron holography

DOE PAGES

Song, Xiaohong; Lin, Cheng; Sheng, Zhihao; ...

2016-06-22

Strong field photoelectron holography has been proposed as a means for interrogating the spatial and temporal information of electrons and ions in a dynamic system. After ionization, part of the electron wave packet may directly go to the detector (the reference wave), while another part may be driven back and scatters off the ion(the signal wave). The interference hologram of the two waves may be used to extract target information embedded in the collision process. Unlike conventional optical holography, however, propagation of the electron wave packet is affected by the Coulomb potential as well as by the laser field. Inmore » addition, electrons are emitted over the whole laser pulse duration, thus multiple interferences may occur. In this work, we used a generalized quantum-trajectory Monte Carlo method to investigate the effect of Coulomb potential and the nonadiabatic subcycle ionization on the photoelectron hologram. Here, we showed that photoelectron hologram can be well described only when the effect of nonadiabatic ionization is accounted for, and Coulomb potential can be neglected only in the tunnel ionization regime. Our results help paving the way for establishing photoelectron holography for probing spatial and dynamic properties of atoms and molecules.« less

An Atmospheric Pressure Chemical Ionization MS/MS Assay Using Online Extraction for the Analysis of 11 Cannabinoids and Metabolites in Human Plasma and Urine.

PubMed

Klawitter, Jelena; Sempio, Cristina; Mörlein, Sophie; De Bloois, Erik; Klepacki, Jacek; Henthorn, Thomas; Leehey, Maureen A; Hoffenberg, Edward J; Knupp, Kelly; Wang, George S; Hopfer, Christian; Kinney, Greg; Bowler, Russell; Foreman, Nicholas; Galinkin, Jeffrey; Christians, Uwe; Klawitter, Jost

2017-10-01

Although, especially in the United States, there has been a recent surge of legalized cannabis for either recreational or medicinal purposes, surprisingly little is known about clinical dose-response relationships, pharmacodynamic and toxicodynamic effects of cannabinoids such as Δ9-tetrahydrocannabinol (THC). Even less is known about other active cannabinoids. To address this knowledge gap, an online extraction, high-performance liquid chromatography coupled with tandem mass spectrometry method for simultaneous quantification of 11 cannabinoids and metabolites including THC, 11-hydroxy-Δ9-tetrahydrocannabinol, 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid, 11-nor-Δ9-tetrahydrocannabinol-9-carboxylic acid glucuronide (THC-C-gluc), cannabinol, cannabidiol, cannabigerol, cannabidivarin, Δ9-tetrahydrocannabivarin (THCV), and 11-nor-9-carboxy-Δ9-tetrahydrocannabivarin (THCV-COOH) was developed and validated in human urine and plasma. In contrast to atmospheric pressure chemical ionization, electrospray ionization was associated with extensive ion suppression in plasma and urine samples. Thus, the atmospheric pressure chemical ionization assay was validated showing a lower limit of quantification ranging from 0.39 to 3.91 ng/mL depending on study compound and matrix. The upper limit of quantification was 400 ng/mL except for THC-C-gluc with an upper limit of quantification of 2000 ng/mL. The linearity was r > 0.99 for all analyzed calibration curves. Acceptance criteria for intrabatch and interbatch accuracy (85%-115%) and imprecision (<15%) were met for all compounds. In plasma, the only exceptions were THCV (75.3%-121.2% interbatch accuracy) and cannabidivarin (interbatch imprecision, 15.7%-17.2%). In urine, THCV did not meet predefined acceptance criteria for intrabatch accuracy. This assay allows for monitoring not only THC and its major metabolites but also major cannabinoids that are of interest for marijuana research and clinical practice.

Oxygen ionization rates at Mars and Venus - Relative contributions of impact ionization and charge exchange

NASA Astrophysics Data System (ADS)

Zhang, M. H. G.; Luhmann, J. G.; Nagy, A. F.; Spreiter, J. R.; Stahara, S. S.

1993-02-01

Oxygen ion production rates above the ionopauses of Venus and Mars are calculated for photoionization, charge exchange, and solar wind electron impact ionization processes. The latter two require the use of the Spreiter and Stahara (1980) gas dynamic model to estimate magnetosheath velocities, densities, and temperatures. The results indicate that impact ionization is the dominant mechanism for the production of O(+) ions at both Venus and Mars. This finding might explain both the high ion escape rates measured by Phobos 2 and the greater mass loading rate inferred for Venus from the bow shock positions.

Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions

NASA Astrophysics Data System (ADS)

Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

2017-07-01

Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO3) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO3-nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO3) was produced in the flame. The HNO3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO3 showed the strongest affinity to histidine and formed (Mhistidine-H+HNO3)- complex ions, whereas some amino acids did not react with HNO3 at all. Reactions between HNO3 and histidine residues in AI and AII resulted in the formation of dominant [MAI-H+(HNO3)]- and [MAII-H+(HNO3)]- ions. Results from analyses of AAs and insulin indicated that HNO3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO3)n]3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins.

Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions.

PubMed

Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

2017-07-01

Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO 3 ) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO 3 -nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO 3 ) was produced in the flame. The HNO 3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO 3 showed the strongest affinity to histidine and formed (M histidine -H+HNO 3 ) - complex ions, whereas some amino acids did not react with HNO 3 at all. Reactions between HNO 3 and histidine residues in AI and AII resulted in the formation of dominant [M AI -H+(HNO 3 )] - and [M AII -H+(HNO 3 )] - ions. Results from analyses of AAs and insulin indicated that HNO 3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO 3 ) n ] 3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins. Graphical Abstract ᅟ.

Wind-embedded shocks in FASTWIND: X-ray emission and K-shell absorption

NASA Astrophysics Data System (ADS)

Carneiro, L. P.; Puls, J.; Sundqvist, J. O.; Hoffmann, T. L.

2017-11-01

EUV and X-ray radiation emitted from wind-embedded shocks can affect the ionization balance in the outer atmospheres of massive stars, and can also be the mechanism responsible for producing highly ionized atoms detected in the wind UV spectra. To investigate these processes, we implemented the emission from wind-embedded shocks and related physics into our atmosphere/spectrum synthesis code FASTWIND. We also account for the high energy absorption of the cool wind, by adding important K-shell opacities. Various tests justfying our approach have been described by Carneiro+(2016, A&A 590, A88). In particular, we studied the impact of X-ray emission on the ionization balance of important elements. In almost all the cases, the lower ionization stages (O iv, N iv, P v) are depleted and the higher stages (N v, O v, O vi) become enhanced. Moreover, also He lines (in particular He ii 1640 and He ii 4686) can be affected as well. Finally, we carried out an extensive discussion of the high-energy mass absorption coefficient, κν, regarding its spatial variation and dependence on T eff. We found that (i) the approximation of a radially constant κν can be justified for r >= 1.2R * and λ <= 18 Å, and also for many models at longer wavelengths. (ii) In order to estimate the actual value of this quantity, however, the He ii background needs to be considered from detailed modeling.

Cassini finds an oxygen-carbon dioxide atmosphere at Saturn's icy moon Rhea.

PubMed

Teolis, B D; Jones, G H; Miles, P F; Tokar, R L; Magee, B A; Waite, J H; Roussos, E; Young, D T; Crary, F J; Coates, A J; Johnson, R E; Tseng, W-L; Baragiola, R A

2010-12-24

The flyby measurements of the Cassini spacecraft at Saturn's moon Rhea reveal a tenuous oxygen (O(2))-carbon dioxide (CO(2)) atmosphere. The atmosphere appears to be sustained by chemical decomposition of the surface water ice under irradiation from Saturn's magnetospheric plasma. This in situ detection of an oxidizing atmosphere is consistent with remote observations of other icy bodies, such as Jupiter's moons Europa and Ganymede, and suggestive of a reservoir of radiolytic O(2) locked within Rhea's ice. The presence of CO(2) suggests radiolysis reactions between surface oxidants and organics or sputtering and/or outgassing of CO(2) endogenic to Rhea's ice. Observations of outflowing positive and negative ions give evidence for pickup ionization as a major atmospheric loss mechanism.

Intact and Top-Down Characterization of Biomolecules and Direct Analysis Using Infrared Matrix-Assisted Laser Desorption Electrospray Ionization Coupled to FT-ICR Mass Spectrometry

PubMed Central

Sampson, Jason S.; Murray, Kermit K.; Muddiman, David C.

2013-01-01

We report the implementation of an infrared laser onto our previously reported matrix-assisted laser desorption electrospray ionization (MALDESI) source with ESI post-ionization yielding multiply charged peptides and proteins. Infrared (IR)-MALDESI is demonstrated for atmospheric pressure desorption and ionization of biological molecules ranging in molecular weight from 1.2 to 17 kDa. High resolving power, high mass accuracy single-acquisition Fourier transform ion cyclotron resonance (FT-ICR) mass spectra were generated from liquid-and solid-state peptide and protein samples by desorption with an infrared laser (2.94 µm) followed by ESI post-ionization. Intact and top-down analysis of equine myoglobin (17 kDa) desorbed from the solid state with ESI post-ionization demonstrates the sequencing capabilities using IR-MALDESI coupled to FT-ICR mass spectrometry. Carbohydrates and lipids were detected through direct analysis of milk and egg yolk using both UV- and IR-MALDESI with minimal sample preparation. Three of the four classes of biological macromolecules (proteins, carbohydrates, and lipids) have been ionized and detected using MALDESI with minimal sample preparation. Sequencing of O-linked glycans, cleaved from mucin using reductive β-elimination chemistry, is also demonstrated. PMID:19185512

Electron induced inelastic and ionization cross section for plasma modeling

NASA Astrophysics Data System (ADS)

Verma, Pankaj; Mahato, Dibyendu; Kaur, Jaspreet; Antony, Bobby

2016-09-01

The present paper reports electron impact total inelastic and ionization cross section for silicon, germanium, and tin tetrahalides at energies varying from ionization threshold of the target to 5000 eV. These cross section data over a wide energy domain are very essential to understand the physico-chemical processes involved in various environments such as plasma modeling, semiconductor etching, atmospheric sciences, biological sciences, and radiation physics. However, the cross section data on the above mentioned molecules are scarce. In the present article, we report the computation of total inelastic cross section using spherical complex optical potential formalism and the estimation of ionization cross section through a semi-empirical method. The present ionization cross section result obtained for SiCl4 shows excellent agreement with previous measurements, while other molecules have not yet been investigated experimentally. Present results show more consistent behaviour than previous theoretical estimates. Besides cross sections, we have also studied the correlation of maximum ionization cross section with the square root of the ratio of polarizability to ionization potential for the molecules with known polarizabilities. A linear relation is observed between these quantities. This correlation is used to obtain approximate polarizability volumes for SiBr4, SiI4, GeCl4, GeBr4, and GeI4 molecules.

Application of Ni-63 photo and corona discharge ionization for the analysis of chemical warfare agents and toxic wastes

NASA Technical Reports Server (NTRS)

Stach, J.; Adler, J.; Brodacki, M.; Doring, H.-R.

1995-01-01

Over the past decade, advances in instrumental design and refinements in the understanding of ion molecule reactions at atmospheric pressure enabled the application of Ion Mobility Spectrometry (IMS) as a simple inexpensive and sensitive analytical method for the detection of organic trace compounds. Positive and negative gas-phase ions for ion mobility spectrometry have been produced by a variety of methods, including photo-ionization, laser multi photon ionization, surface ionization, corona discharge ionization. The most common ion source used in ion mobility spectrometry is a radioactive Ni-63 foil which is favored due to simplicity, stability, convenience, and high selectivity. If reactant ions like (H2O(n)H)(+) or (H2O(n)O2)(-) dominate in the reaction region, nearly all kinds of compounds with a given proton or electron affinity; are ionized. However, the radioactivity of the Ni-63 foil is one disadvantage of this ion source that stimulates the development and application of other ionization techniques. In this paper, we report analyses of old chemical warfare agents and toxic wastes using Bruker RAID ion mobility spectrometers. Due to the modular construction of the measuring cell, the spectrometers can be equipped with different ion sources. The combined use of Ni-63, photo- and corona discharge ionization allows the identification of different classes of chemical compounds and yields in most cases comparable results.

Ionospheres of the terrestrial planets

NASA Astrophysics Data System (ADS)

Schunk, R. W.; Nagy, A. F.

1980-11-01

The theory and observations relating to the ionospheres of the terrestrial planets Venus, the earth, and Mars are reviewed. Emphasis is placed on comparing the basic differences and similarities between the planetary ionospheres. The review covers the plasma and electric-magnetic field environments that surround the planets, the theory leading to the creation and transport of ionization in the ionospheres, the relevant observations, and the most recent model calculations. The theory section includes a discussion of ambipolar diffusion in a partially ionized plasma, diffusion in a fully ionized plasma, supersonic plasma flow, photochemistry, and heating and cooling processes. The sections on observations and model calculations cover the neutral atmosphere composition, the ion composition, the electron density, and the electron, ion, and neutral temperatures.

Ionization and excitation in cool giant stars. I - Hydrogen and helium

NASA Technical Reports Server (NTRS)

Luttermoser, Donald G.; Johnson, Hollis R.

1992-01-01

The influence that non-LTE radiative transfer has on the electron density, ionization equilibrium, and excitation equilibrium in model atmospheres representative of both oxygen-rich and carbon-rich red giant stars is demonstrated. The radiative transfer and statistical equilibrium equations are solved self-consistently for H, H(-), H2, He I, C I, C II, Na I, Mg I, Mg II, Ca I, and Ca II in a plane-parallel static medium. Calculations are made for both radiative-equilibrium model photospheres alone and model photospheres with attached chromospheric models as determined semiempirically with IUE spectra of g Her (M6 III) and TX Psc (C6, 2). The excitation and ionization results for hydrogen and helium are reported.

Determination of hexabromocyclododecane by flowing atmospheric pressure afterglow mass spectrometry.

PubMed

Smoluch, Marek; Silberring, Jerzy; Reszke, Edward; Kuc, Joanna; Grochowalski, Adam

2014-10-01

The first application of a flowing atmospheric-pressure afterglow ion source for mass spectrometry (FAPA-MS) for the chemical characterization and determination of hexabromocyclododecane (HBCD) is presented. The samples of technical HBCD and expanded polystyrene foam (EPS) containing HBCD as a flame retardant were prepared by dissolving the appropriate solids in dichloromethane. The ionization of HBCD was achieved with a prototype FAPA source. The ions were detected in the negative-ion mode. The ions corresponding to a deprotonated HBCD species (m/z 640.7) as well as chlorine (m/z 676.8), nitrite (m/z 687.8) and nitric (m/z 703.8) adducts were observed in the spectra. The observed isotope pattern is characteristic for a compound containing six bromine atoms. This technique is an effective approach to detect HBCD, which is efficiently ionized in a liquid phase, resulting in high detection efficiency and sensitivity. Copyright © 2014 Elsevier B.V. All rights reserved.

Consistent transport coefficients in astrophysics

NASA Technical Reports Server (NTRS)

Fontenla, Juan M.; Rovira, M.; Ferrofontan, C.

1986-01-01

A consistent theory for dealing with transport phenomena in stellar atmospheres starting with the kinetic equations and introducing three cases (LTE, partial LTE, and non-LTE) was developed. The consistent hydrodynamical equations were presented for partial-LTE, the transport coefficients defined, and a method shown to calculate them. The method is based on the numerical solution of kinetic equations considering Landau, Boltzmann, and Focker-Planck collision terms. Finally a set of results for the transport coefficients derived for a partially ionized hydrogen gas with radiation was shown, considering ionization and recombination as well as elastic collisions. The results obtained imply major changes is some types of theoretical model calculations and can resolve some important current problems concerning energy and mass balance in the solar atmosphere. It is shown that energy balance in the lower solar transition region can be fully explained by means of radiation losses and conductive flux.

Cosmogenic Secondary Radiation from a Nearby Supernova

NASA Astrophysics Data System (ADS)

Overholt, Andrew

2017-01-01

Increasing evidence has been found for multiple supernovae within 100 pc of the solar system. Supernovae produce large amounts of cosmic rays which upon striking Earth's atmosphere, produce a cascade of secondary particles. Among these cosmic ray secondaries are neutrons and muons, which penetrate far within the atmosphere to sea level and even below sea level. Muons and neutrons are both forms of ionizing radiation which have been linked to increases in cancer, congenital malformations, and other maladies. This work focuses on the impact of muons, as they penetrate into ocean water to impact the lowest levels of the aquatic food chain. We have used monte carlo simulations (CORSIKA, MCNPx, and FLUKA) to determine the ionizing radiation dose due to cosmic ray secondaries. This information shows that although most astrophysical events do not supply the necessary radiation flux to prove dangerous; there may be other impacts such as an increase to mutation rate.

Characterization of polymethoxylated flavones in Fructus aurantii by liquid chromatography with atmospheric pressure chemical ionization combined with tandem mass spectrometry.

PubMed

Zhou, Da-Yong; Chen, De-Liang; Xu, Qing; Xue, Xing-Ya; Zhang, Fei-Fang; Liang, Xin-Miao

2007-04-11

Atmospheric pressure chemical ionization mass spectrometry (APCI-MS) was operated in positive mode (PI) to characterize polymethoxylated flavonoids (PMFs) through its specific radical cations by collision-induced dissociation (CID). The fragments of [M + H - n x 15]+ produced by loss of one or more methyl group from the protonated molecule, as well as [M + H - 29]+, [M + H - 31]+, [M + H - 33]+, [M + H - 43]+, [M + H - 46]+, and [M + H - 61]+ fragment ions were detected, which were diagnostic for the polymethoxylated species, and could be adopted to form the multiple MS (MS(n)) "fingerprint" of PMFs. Based on this "fingerprint", 29 PMFs were screened out from extracts of Fructus aurantii, among which two of them were identified as sinensetin and tangeretin. It was proved that the PI was suitable for structural characterization of PMFs by APCI-MS(n).

A sensitive gas chromatography detector based on atmospheric pressure chemical ionization by a dielectric barrier discharge.

PubMed

Kirk, Ansgar T; Last, Torben; Zimmermann, Stefan

2017-02-03

In this work, we present a novel concept for a gas chromatography detector utilizing an atmospheric pressure chemical ionization which is initialized by a dielectric barrier discharge. In general, such a detector can be simple and low-cost, while achieving extremely good limits of detection. However, it is non-selective apart from the use of chemical dopants. Here, a demonstrator manufactured entirely from fused silica capillaries and printed circuit boards is shown. It has a size of 75×60×25mm 3 and utilizes only 2W of power in total. Unlike other known discharge detectors, which require high-purity helium, this detector can theoretically be operated using any gas able to form stable ion species. Here, purified air is used. With this setup, limits of detection in the low parts-per-billion range have been obtained for acetone. Copyright © 2017 Elsevier B.V. All rights reserved.

Balloon-borne photoionization mass spectrometer for measurement of stratospheric gases

NASA Technical Reports Server (NTRS)

Aikin, A. C.; Maier, E. J. R.

1978-01-01

A balloon-borne photoionization mass spectrometer used to measure stratospheric trace gases is described. Ions are created with photons from high-intensity krypton discharge lamps and a quadrupole mass analyzer is employed for ion identification. Differential pumping is achieved with liquid helium cryopumping. To insure measurement of unperturbed stratospheric air, the entire system is contained in a sealed gondola and the atmospheric sample is taken some distance away during descent. The photoionization technique allows the detection of a low ionization potential constituent, such as nitric oxide, at less than a part in one billion in the presence of the major atmospheric gases and their isotopes. Operation of the mass spectrometer system was demonstrated during a daytime flight from Palestine, Texas on 26 April 1977. The sensitivity achieved and the unique selectivity afforded by this technique offer a capability for trace constituent measurement not possible with the more conventional electron impact ionization approach.