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Chemical Differences between Phenolic Secondary Organic Aerosol Formed through Gas-Phase and Aqueous-Phase Reactions

Phenolic compounds, which are significant emissions from biomass burning (BB), undergo rapid photochemical reactions in both gas and aqueous phases to form secondary organic aerosol, namely, gasSOA and aqSOA, respectively. The formation of gasSOA and aqSOA involves different reaction mechanisms, leading to different product distributions. In this study, we investigate the gaseous and aqueous reactions of guaiacol a representative BB phenol to elucidate the compositional differences between phenolic aqSOA and gasSOA. Aqueous-phase reactions of guaiacol produce higher SOA yields than gas-phase reactions (e.g., roughly 60 vs 30% at one half-life of guaiacol). These aqueous reactions involve more complex reaction mechanisms and exhibit a more gradual SOA evolution than their gaseous counterparts. Initially, gasSOA forms with high oxidation levels (O/C > 0.82), while aqSOA starts with lower O/C (0.55–0.75). However, prolonged aqueous-phase reactions substantially increase the oxidation state of aqSOA, making its bulk chemical composition closer to that of gasSOA. Additionally, aqueous reactions form a greater abundance of oligomers and high-molecular-weight compounds, alongside a more sustained production of carboxylic acids. AMS spectral signatures representative of phenolic gasSOA have been identified, which, together with tracer ions of aqSOA, can aid in the interpretation of field observation data on aerosol aging within BB smoke. The notable chemical differences between phenolic gasSOA and aqSOA highlighted in this study also underscore the importance of accurately representing both pathways in atmospheric models to better predict the aerosol properties and their environmental impacts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Representation of the Geosynchronous Plasma Environment for Spacecraft Charging Calculations

Historically, our ability to predict and postdict surface charging has suffered from both a lack of reliable secondary emission and backscattered electron yields and poor characterization of the plasma environment. One difficulty lies in the common practice of fitting the plasma data to a Maxwellian or Double Maxwellian distribution function, which may not represent the data well for charging purposes. For 13 years Los Alamos National Laboratory (LANL) has been accumulating measurements of electron and proton spectra from Magnetospheric Plasma Analyzer (MPA) instruments aboard a series of geosynchronous satellites. These data provide both a plasma characterization and the potential of the instrument ground. We use electron and ion flux spectra measured by the LANL MPA to examine how the use of different spectral representations of the charged particle environment in computations of spacecraft potentials during magnetospheric substorms affects the accuracy of the results. We calculate the spacecraft potential using both the measured fluxes and several different fits to these fluxes. These flux measurements and fits have been corrected for the difference between the measured and calculated potential. The potentials computed using the measured fluxes, the best available material properties of graphite carbon, and a secondary electron escape fraction of 81%, are within a factor of three of the measured potential for nearly all the data. Using a Kappa fit to the electron distribution function and a Maxwellian fit to the ion distribution function gives agreement similar to the calculations using the actual data. Alternative spectral representations, including Maxwellian and double Maxwellian for both species, lead to less satisfactory agreement between predicted and measured potentials.

Davis, V. A.↗

An optical region elemental abundance analysis of the chemically peculiar HgMn star chi Lupi

The optical spectrum of the chemically peculiar HgMn type binary star chi Lupi has been analyzed to determine atmospheric parameters and elemental abundances. Echelle spectra were obtained with the 3.9 m Anglo-Australian telescope to exploit the extreme shape-lined nature of the spectrum. This study was undertaken in support of ultraviolet analyses currently underway that utilize echell spectra obtained with the Hubble Space Telescope. For the B9.5 V primary star we obtain T(sub eff) = 10650 K, log g = 3.9, and xi = 0 km/s, while for the A2 V secondary, T(sub eff) = 9200 K, log g = 4.0, and xi = 2 km/s. Most of the elemental abundances are typical of HgMn stars with similar T(sub eff) showing an overall iron-peak elemental abundance distribution that is basically solar in nature with enhancement of the light elements Si, P, and S, as well as all detected elements heavier than the iron group. Abundances for several elements have been determined for the first time in this star, including several of the rare-earths. The secondary star spectrum shows Am star characteristics. We also discuss the relative merits of the equivalent width and synthetic spectrum techniques in determining the elemental abundences, concluding that the synthetic spectrum technique is necessary for obtaining abundances with the utmost accuracy.

Wahlgren, Glenn M.↗

Heat transfer from glass melt to cold cap: Computational fluid dynamics study of cavities beneath cold cap

Efficient glass production depends on the continuous supply of heat from the glass melt to the floating layer of batch, or cold cap. Computational fluid dynamics (CFD) are employed to investigate the formation and behavior of gas cavities that form beneath the batch by gases released from the collapsing primary foam bubbles, ascending secondary bubbles, and in the case of forced bubbling, from the rising bubbling gas. The gas phase fraction, temperature, and velocity distributions below the cold cap are used to calculate local and average heat transfer rates as a function of the bubbling rate. It is shown that the thickness of the cavities is nearly independent of the cold cap shape and the amount of foam evolved during batch conversion. Furthermore, it is ~7 mm and up to ~15 mm for the cases without and with forced bubbling used to promote circulation within the melt, respectively. Using computed velocity and temperature profiles, the melting rate of the simulated high-level nuclear waste glass batch was estimated to increase with the bubbling rate to the power of ~0.3 to 0.9, depending on the flow pattern. The simulation results are in good agreement with experimental data from laboratory- and pilot-scale melter tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Interregional Renewable Energy Zones

Interregional Renewable Energy Zones (IREZs) are a component of the National Transmission Planning Study (NTPS), which analyzes strategies for building out transmission infrastructure to support decarbonizing the electricity sector by 2035. In particular, IREZs envision long-distance transmission corridors for moving large amounts of low-cost renewable energy. An IREZ is a transmission collection point that is easily accessible to a very high volume of low-cost developable wind and solar energy potential. This dataset includes 155 IREZs identified across the continental United States where each IREZ is characterized by its primary and secondary resource.

24 POWER TRANSMISSION AND DISTRIBUTION↗

ISEE-1 and ISEE-2 fast plasma experiment and the ISEE-1 solar wind experiment

Identical fast plasma experiment (FPE) systems were placed on the ISEE-1 and ISEE-2 spacecraft. The FPE consists of three high efficiency 90 deg spherical section electrostatic analyzers using large secondary emitters and discrete dynode multipliers to detect analyzed particles. Two of them, viewing in opposite directions, produce complete 2D velocity distribution measurements of both protons and electrons every spacecraft revolution. A third FPE analyzer with a divided emitter measures 3D distributions at a slower rate. ISEE-1 also carries a solar-wind experiment (SWE) to measure solar-wind ions with high resolution. The SWE is composed of two 150 deg spherical section analyzers using the same set of plates. The two acceptance fans are tilted with respect to each other so that 3D characteristics of the ion distributions can be derived.

Bame, S. J.↗

Computation of three-dimensional flow in turbofan mixers and comparison with experimental data

A three dimensional, viscous computer code was used to calculate the mixing downstream of a typical turbofan mixer geometry. Experimental data obtained using pressure and temperature rakes at the lobe and nozzle exit stations were used to validate the computer results. The relative importance of turbulence in the mixing phenomenon as compared with the streamwise vorticity set up by the secondary flows was determined. The observations suggest that the generation of streamwise vorticity plays a significant role in determining the temperature distribution at the nozzle exit plane.

Povinelli, L. A.↗

Computation of three-dimensional flow in turbofan mixers and comparison with experimental data

A three-dimensional, viscous computer code was used to calculate the mixing downstream of a typical turbofan mixer geometry. Experimental data were obtained using pressure and temperature rakes at the lobe and nozzle exit stations. Secondary flow velocities were also obtained. These data were used to validate the computer results. An assessment was also made to determine the relative importance of turbulence in the mixing phenomenon as compared with the streamwise vorticity set up by the secondary flows. The observations suggest that the generation of streamwise vorticity appears to play a significant role in determining the temperature distribution at the nozzle exit plane.

Povinelli, L. A.↗

Radar altimetry of South Tharsis, Mars

The paper discusses Martian altitudes measured by radar during the oppositions of 1971 and 1973 using the 64-m antenna at Goldstone, Calif. The resultant topographic profiles substantiate a zonal classification of the volanic flows blanketing the south flanks of Arsia Mons, and they confirm the existence of a secondary, parasitic shield, attached from the SSW to the main Arsia shield. The secondary shield is about 400 km in diameter at its base and at least 4 km high at its center. The distribution and orientation of the lunar mare - like ridges in Sinai Planum appear to be independent of the regional gradients. Segments of the chaotic terrain at the eastern terminus of Valles Marineris are located down to 6 km below the level of the surrounding plains.

Roth, L. E.↗

Interdisciplinary Determination of Ice Sheet Accumulation Patterns: Combined Atmospheric Modeling and Field and Remote Sensing Studies

This research is focusing on two related areas that are fundamental to the NASA PARCA (Program for Arctic Regional Climate Assessment) program. The primary research area is the determination of the amount, rate, and timing of accumulation at distributed sites in the dry snow zone of Greenland and evaluation of these results in light of accumulation modeling results. The secondary research area is the calibration of the isotope "thermometer" at these ice sheet sites as well as the determination of long-term temperature trends in Greenland.

Shuman, C. A.↗

Calculational and Experimental Investigations of the Pressure Effects on Radical - Radical Cross Combinations Reactions: C2H5 + C2H3

Pressure-dependent product yields have been experimentally determined for the cross-radical reaction C2H5 + C2H3. These results have been extended by calculations. It is shown that the chemically activated combination adduct, 1-C4H8*, is either stabilized by bimolecular collisions or subject to a variety of unimolecular reactions including cyclizations and decompositions. Therefore the "apparent" combination/disproportionation ratio exhibits a complex pressure dependence. The experimental studies were performed at 298 K and at selected pressures between about 4 Torr (0.5 kPa) and 760 Torr (101 kPa). Ethyl and vinyl radicals were simultaneously produced by 193 nm excimer laser photolysis of C2H5COC2H3 or photolysis of C2H3Br and C2H5COC2H5. Gas chromatograph/mass spectrometry/flame ionization detection (GC/MS/FID) were used to identify and quantify the final reaction products. The major combination reactions at pressures between 500 (66.5 kPa) and 760 Torr are (1c) C2H5 + C2H3 yields 1-butene, (2c) C2H5 + C2H5 yields n-butane, and (3c) C2H3 + C2H3 yields 1,3-butadiene. The major products of the disproportionation reactions are ethane, ethylene, and acetylene. At moderate and lower pressures, secondary products, including propene, propane, isobutene, 2-butene (cis and trans), 1-pentene, 1,4-pentadiene, and 1,5-hexadiene are also observed. Two isomers of C4H6, cyclobutene and/or 1,2-butadiene, were also among the likely products. The pressure-dependent yield of the cross-combination product, 1-butene, was compared to the yield of n-butane, the combination product of reaction (2c), which was found to be independent of pressure over the range of this study. The [ 1-C4H8]/[C4H10] ratio was reduced from approx.1.2 at 760 Torr (101 kPa) to approx.0.5 at 100 Torr (13.3 kPa) and approx.0.1 at pressures lower than about 5 Torr (approx.0.7 kPa). Electronic structure and RRKM calculations were used to simulate both unimolecular and bimolecular processes. The relative importance of C-C and C-H bond ruptures, cyclization, decyclization, and complex decompositions are discussed in terms of energetics and structural properties. The pressure dependence of the product yields were computed and dominant reaction paths in this chemically activated system were determined. Both modeling and experiment suggest that the observed pressure dependence of [1-C4H8]/[C4H10] is due to decomposition of the chemically activated combination adduct 1-C4H8* in which the weaker allylic C-C bond is broken: H2C=CHCH2CH3 yields C3H5 + CH3. This reaction occurs even at moderate pressures of approx.200 Torr (26 kPa) and becomes more significant at lower pressures. The additional products detected at lower pressures are formed from secondary radical-radical reactions involving allyl, methyl, ethyl, and vinyl radicals. The modeling studies have extended the predictions of product distributions to different temperatures (200-700 K) and a wider range of pressures (10(exp -3) - 10(exp 5) Torr). These calculations indicate that the high-pressure [1-C4H8]/[C4H10] yield ratio is 1.3 +/- 0.1.

Fahr, Askar↗

A Historical Perspective on Primary and Possible Secondary Sources of Atmospheric Carbon Tetrachloride

Atmospheric sources of Carbon Tetrachloride (CTC) have been controversial since its detection in the early 1970. Initial proposals were that it is globally uniformly distributed and its lack of current emissions and inferred lifetime indicated that it was likely of natural origin. Historical analysis of CTC use and emissions showed that atmospheric CTC was long-lived and mainly of man-made origin although small natural sources and sinks (e. g. oceans) could not be ruled out. This deduction was hard because a majority of emissions had occurred in early part of the 20th century when CTC was commonly used as a fumigant, a solvent, and a raw material for the manufacture of many chemicals. In the 1940's adverse health effects of exposure to CTC became evident and its emissions were greatly curtailed and substituted with C2Cl4 which was thought to be much safer. There were smog chamber studies that showed that C2Cl4, a widely used solvent during the late 20th century, could produce CTC with up to a 7% yield. Subsequently it was discovered that this chemistry probably required Cl atoms and since Cl atoms were not abundant in the atmosphere actual yields based on OH oxidation were probably closer to 0.1%. CTC was subsequently banned by the Montreal Protocol to prevent stratospheric ozone depletion and its preferred substitute C2Cl4 was also banned by EPA for reasons of potential carcinogenicity and toxicity. CTC since has been measured in many airborne NASA campaigns in which plumes have been sampled from a variety of regions which may still be emitting CTC. I will briefly discuss this historical perspective of CTC and show some recent data that may shed light on its current sources or lack there off.

atmosphere↗

Evolution of the Far-Infrared Cloud at Titan's South Pole

A condensate cloud on Titan identified by its 220 cm−1 far-infrared signature continues to undergo seasonal changes at both the north and south poles. In the north, the cloud, which extends from 55 N to the pole, has been gradually decreasing in emission intensity since the beginning of the Cassini mission with a half-life of 3.8 years. The cloud in the south did not appear until 2012 but its intensity has increased rapidly, doubling every year. The shape of the cloud at the south pole is very different from that in the north. Mapping in 2013 December showed that the condensate emission was confined to a ring with a maximum at 80 S. The ring was centered 4deg from Titanʼs pole. The pattern of emission from stratospheric trace gases like nitriles and complex hydrocarbons (mapped in 2014 January) was also offset by 4deg, but had a central peak at the pole and a secondary maximum in a ring at about 70 S with a minimum at 80 S. The shape of the gas emission distribution can be explained by abundances that are high at the atmospheric pole and diminish toward the equator, combined with correspondingly increasing temperatures. We discuss possible causes for the condensate ring. The present rapid build up of the condensate cloud at the south pole is likely to transition to a gradual decline from 2015 to 2016. Key words: molecular processes - planets and satellites: atmospheres - planets and satellites: composition - planets and satellites: individual (Titan) - radiation mechanisms: thermal

Cassini↗

In Vitro Experimental Model to Investigate the Biological Effects across the Bragg Curve of High-LET Radiation

The space environment consists of a varying field of radiation particles including high energy ions, with a spacecrafts shielding material providing the only major protection to astronauts from harmful exposure. Unlike lowLET gamma or Xrays, the presence of shielding does not always reduce the radiation risks for energetic charged particle exposure since the dose delivered by the charged particle increases sharply as the particle approaches the end of its range, a position known as the Bragg peak and the correlating spatial dose distribution identified as the Bragg curve. The Bragg curve does not necessarily represent the biological damage along the particle traversal since biological effects are influenced by the track structure of both primary and secondary particles. Therefore, the biological Bragg curve is dependent of the energy and the type of the primary particle, and may vary for different biological endpoints. Here we describe a unique irradiation geometry and experimental system to measure the biological response across the Bragg curve in one consistent biological sample. Polyethylene shielding was used to achieve a Bragg curve distribution with the beam geometry parallel to a monolayer of fibroblast cells. We present data that highlights the differential formation of DNA double strand breaks (DSBs) and chromosomal deletions across the Bragg curve in human fibroblasts irradiated with 600 MeV/nucleon iron ion beams. Qualitative analyses of gammaH2AX fluorescence, a known marker of DSBs, indicated potentially increased clustering of DNA damage before the Bragg peak, enhanced homogenous distribution at the peak, and provided visual evidence of high linear energy transfer (LET) particle traversal of cells beyond the Bragg peak in agreement with one-dimensional transport approximations. A biological response curve generated for micronuclei induction across the Bragg curve for 600 MeV/n Fe ions did not reveal an increase in the yield of micronuclei at the Bragg peak location. Assessment of such biological parameters employing the described in vitro experimental system may provide improved platforms to measure a number of biological consequences of shielding materials across the Bragg curve for high charge and energy (HZE) ions.

Desai, N.↗

Effects of Multiple Nozzles on Asymmetric Ejector Performance

This paper presents a comparison of a single nozzle and a dual nozzle strut based ejector. The results are focused on the fluid properties in the ejector duct. The research focused on choking mechanisms, mass flow entrainment, and mixing duct pressure distributions. The two ejectors were tests at equivalent primary mass flow rates. This corresponds to chamber pressures ranging from 100 psi to 900 psi in the single nozzle strut and 50 psi to 450 psi in the dual nozzle strut. Secondary flow was drawn from the lab at atmospheric pressure, and was not controlled. The secondary flow was found to choke at a value of 2.3 lb/s for a primary mass flow rate at approximately 2.1 lb/s for both ejectors. This choke was believed to be a mass addition choke rather than a traditional aerodynamic choke. The mixing duct pressure distribution exhibited two distinct trends at "low pressure" trend and at "high pressure" trend. For the low pressure trend, the mixing length for the ejectors remained fixed around 20 inches, regardless of the chamber pressure. For the higher pressure trend, the mixing length was considerably longer and increased with increasing chamber pressure. At high chamber pressures (high mass flow rates), a supersonic core flow was present at the exit of the duct. For these cases, the two streams did not have time to mix by the end of the duct.

Lineberry, D.↗

Dark Matter in the Universe and in the Galaxy

During the past four years, Prof. Kamionkowski and collaborators have made progress in research on the nature and distribution of dark-matter in the Universe and in the Galaxy, and on related topics in astrophysics and cosmology. We have made progress on research on the cosmic microwave background, large-scale structure, issues related to particle dark matter, and the gamma-ray-burst enigma. A significant fraction of the research supported by this ATP has been on the cosmic microwave background (CMB). Prof. Kamionkowski and collaborators showed how the polarization of the CMB could be used to detect long-wavelength gravitational waves, such as those produced by inflation. With Kosowsky, Prof. Kamionkowski calculated the amplitude of a stochastic gravitational-wave background that could be detected for a satellite experiment of a given sensitivity and angular resolution. They showed that polarization should improve the sensitivity oa MAP to these gravity waves, and that the Planck Surveyor should do even better. Prof. Kamionkowski, Caldwell, and a student calculated and illustrated the CMB temperature/polarization pattern produced by a single plane-wave gravitational wave. They calculated the amplitude of such a wave that would be detectable with MAP and Planck, and compared that with the sensitivity of traditional gravitational-wave detectors like LIGO and LISA. With Lue and Wang, the PI showed how parity violation from new high-energy physics could conceivably give rise to an observable signature in the CMB polarization. With Loeb, Prof. Kamionkowski showed how measurement of the polarization of CMB photons scattered by hot gas in a cluster could be used to determine the quadrupole moment of the CMB incident on that cluster. Prof. Kamionkowski and Jaffe calculated the amplitude of secondary anisotropies produced by scattering of CMB photons from reionized regions. Research has also been carried out on probing the large-scale distribution of mass in the Universe today, and on structure-formation theories. They investigated the possibility of determining the large-scale distribution of mass in the Universe via measurement of ellipticity-ellipticity correlations in the FIRST radio survey induced by weak gravitational lensing due to mass inhomogeneities along the line of sight. Dr. Summers, Prof. Kamionkowski, and a student investigated the distribution of protogalactic masses and angular momenta in an effort to understand how the luminosity function and angular-momentum distribution of disk galaxies arises from an initial power spectrum of density perturbations. Several projects related to the distribution and possible detection of dark matter in our Galactic halo were studied. The PI was involved in several projects involving the calculation of nuclear-reaction rates needed for stellar evolution and for predictions of solar-neutrino fluxes.

Kamionkowski, Marc↗

Another look at equatorial metallic ions in the F region

An extensive survey is made of the equatorial occurrences of the Fe+ ion as detected by the ion mass spectrometer on the Atmospheric Explorer E. The longest time period (4 years) data base available for the study of the equatorial metallic ion distributions is considered, as well as Fe+ concentrations exceeding 10, 30, and 100 per cubic cm. The number of occurrences in the F region are most frequent at the dayside dip equator. Diurnally, the events are not appreciable in the F region until a few hours after dawn, reaching a maximum near noon followed by a secondary maximum in the afternoon. Near and after dusk the Fe+ ions extended on the average to higher altitudes than during the day and became less and less frequent from midnight to dawn. Seasonally, the distributions between 200 and 300 km are skewed away from the dip equator during the day with the maximum frequency of occurrence north (south) of the dip equator during a period centered on the December (June) solstice.

Grebowsky, J. M.↗

Propagation of injected cosmic rays under distributed reacceleration

The cosmic ray acceleration model in which the particles gain continuously energy from stochastic processes in the interstellar space by encountering shocks leads to a logarithmic increase in the secondary to primary ratios with energy, which is inconsistent with observations. The observed decrease of the secondary to primary ratios may therefore suggest that a considerable part of the acceleration has taken place rapidly at the sources. Astronomical observations on the other hand indicate that shocks from supernovae do exist in the galaxy and observations in the interplanetary space show clear evidence that shock acceleration works.

Simon, M.↗