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1,757 records · Page 98

Laser Prevention of Earth Impact Disasters

Today we are seeing the geological data base constantly expanding as new evidence from past impacts with the Earth are discovered and investigated. It is now commonly believed that a hypervelocity impact occurring approximately 65 million years ago in the Yucatan Peninsula area was the disaster responsible for the extinction of almost 70% of the species of life on Earth including of course the dinosaurs. What is sobering is that we believe now that this was just one of several such disasters and that some of the others caused extinctions to even a greater extent. Preventing collisions with the Earth by hypervelocity asteroids, meteoroids, and comets is the most important problem facing human civilization. While there are many global problems facing our planet including overpopulation, pollution, disease, and deforestation; none of these offer the potential of rapid, total extinction. Rapid is the operative word here in that many of the global problems we face may indeed, if not sufficiently addressed, pose a similar long-term threat. However, with the impact threat, a single, almost unpredictable event could lead to a chain reaction of disasters that would end everything mankind has worked to achieve over the centuries. Our chances of being hit are greater than our chance of winning the lottery. We now believe that while there are only about 2000-earth orbit crossing rocks great than 1 kilometer in diameter, there may be as many as 100,000 rocks in the 100 m size range. The 1 kilometer rocks are difficult to detect and even harder to track. The 100 m class ones are almost impossible to find with today's technology. Can anything be done about this fundamental existence question facing us? The answer is a resounding yes. By using an intelligent combination of Earth and space based sensors coupled with high-energy laser stations in orbit, we can deflect rocks from striking the Earth. This is accomplished by irradiating the surface of the rock with sufficiently intense pulses so that ablation occurs. This ablation acts as a small rocket incrementally changing the shape of the rock's orbit around the Sun.

Campbell, Jonathan W.↗

Exploring the Production of NOx by Lightning and Its Impact on Tropospheric Ozone

Our quantitative understanding of free tropospheric (FT) chemistry is quite poor. State-of-the-art regional air quality models (e.g., US EPA's CMAQ) perform very poorly in simulating FT chemistry, with Uniform ozone around 70 ppb throughout the FT in summer, while ozonesonde data show much higher levels of ozone and much spatial-temporal structure. Such models completely neglect lightning-NOx (LNOx) emissions (the most significant source of NOx in the FT), and also contain large uncertainties in the specifications of intercontinental transport, stratosphere-troposphere exchange (STE) and PBLFT exchange (PFTE). Global air chemistry models include LNOx, but in very crude fashion, with the frequency and distribution of lightning being based on modeled cloud parameters (hence large uncertainty), lightning energetics being assumed to be constant for all flashes (literature value, while in reality there is at least a two-orders of magnitude variability from flash-to-flash), and the production of NOx in the surrounding heated air, per Joule of heating, being assumed to be constant also (literature value, while in fact it is a non-linear function of the dissipated heat and local air density, p). This situation is commonly blamed on paucity of pertinent observational data, but for the USA, there is now a wealth of surface- and satellite-based data of lightning available to permit much improved observation-based estimation of LNOx emissions. In the FT, such NOx has a long residence time, and also the ozone production efficiency from NOx there is considerably higher than in the PBL. It is, therefore, of critical importance in FT chemistry. This paper will describe the approach and data products of an ongoing NSSTC project aimed at a much-improved quantification of not only LNOx production on the scale of continental USA based on local and regional lightning observations, but also of intercontinental transport, STE and PFTE, all in upgraded simulations of tropospheric transport and chemistry. In our approach for LNOx, (a) we utilize continuous observed lightning information from the NLDN ground network and from satellite imagers (OTD and LIS) to quantify lightning frequency and distribution at the spatial-temporal scales of models such as CMAQ; (b) we develop new methodologies to quantify flash-specific lightning energy dissipation as heat (epsilon) using data from the research-grade lightning measurement facility at NASA-KSC, and to parameterize epsilon based on regional lightning monitoring data (ground- and satellite-based); and, (c) we develop a new parameterization of NOx production as a function of epsilon and rho. Based on such observation-based information, we are working to develop a gridded, episodic LNOx emissions inventory for the USA for use in models like CMAQ. We are also developing approaches for global(MOZART)- regional(CMAQ) chemistry coupling to improve intercontinental transport and STE. Finally, we are developing new methodologies for assimilation of satellite-observed (GOES) clouds into meteorological modeling (MM5), to improve PFTE and to optimize co-location of cloud convection and observed lightning. We will incorporate these improvements in CMAQ simulations over the USA to better understand FT processes and chemistry, and its impact on ground-level ozone.

Gillani, Noor↗

Uncovering New Physics in the Cosmic Microwave Background: Developing Novel Theoretical Models and Machine-Learning-Powered Constraints

The search for evidence of new physics via its signatures in the cosmos is a cornerstone goal of the Office of High Energy Physics in the DOE Office of Science. Indeed, the current concordance cosmological model provides intriguing hints for beyond-the-standard-model (BSM) physics, such as dark matter and dark energy. Recently, a potential breakdown has appeared in this model, which could be initial evidence toward a further important revision in our fundamental theoretical understanding of cosmology. This breakdown is reflected in disagreements between inferences of the current expansion rate of the universe, H 0 (the Hubble constant), based on indirect, cosmological data (e.g., from the early universe) and based on direct, local measurements. Despite significant effort, a compelling new concordance cosmological model has yet to be found; achieving significant progress on this front was the first major focus of the project. Theoretical considerations indicate that if the observational discrepancies are not due to systematic errors, they strongly suggest new physics operating in the redshift range just prior to recombination, when cosmic microwave background (CMB) photons last scattered. Crucially, almost all such models produce unique signatures in the CMB temperature and polarization power spectra, which will be measured with unprecedented precision by ongoing and upcoming experiments, including the DOE-supported CMB-S4 project. However, these subtle hints of new physics must be uncovered from beneath a swath of Galactic and extragalactic foreground contamination. Current CMB analysis methods, although powerful, do not optimally infer the CMB power spectrum in the presence of non-Gaussian foregrounds. There is thus scope for theoretical improvement in this foundational challenge of cosmological inference, which formed the second major focus of the project. The primary objectives of the project were two-fold: (1) to develop new theoretical models in cosmology that can restore concordance amongst the full suite of cosmological data sets, thereby potentially providing evidence of novel BSM physics; (2) to develop new theoretical machinery to enable significant sensitivity improvements in searches for new physics in cosmology, particularly via the CMB power spectrum. The two objectives are intertwined, as the analysis methodology improvements in (2) will enable the tightest possible constraints on the signatures of new physics predicted by the novel scenarios in (1). The theoretical approaches to restore concordance focused on models involving novel scalar field dynamics in the pre-recombination universe (the “early dark energy” scenario and modifications thereof), as well as couplings between this field and other components in the standard cosmological model, such as dark matter. We also studied a model featuring a generalization of the decaying dark matter scenario, in which a sub-component of dark matter converts into dark radiation at late times in cosmic history. While these ideas are mostly driven by phenomenological considerations, this tactic has proven extremely successful in cosmology throughout the past few decades, including in the early history of evidence for dark matter and dark energy. The new theoretical machinery envisioned in (2) is undergirded by developments in signal processing and machine learning, which will enable improvements in CMB power spectrum estimation in the presence of non-Gaussian foreground contaminants. In turn, this will yield optimal sensitivity in searches for new physics in the CMB, by maximizing the cosmological information that is extracted from this observable. The most ambitious outcome of this work would be the construction of a new cosmological model that restores concordance amongst data sets. Although the individual models studied here did not fully achieve that goal, significant progress in narrowing down the model space was made, as described below. Moreover, the outcome of the methodological improvements in (2) will significantly impact a wide range of theoretical cosmology, by enabling the tightest possible constraints on any model that leaves novel signatures in the CMB temperature and polarization power spectra.

79 ASTRONOMY AND ASTROPHYSICS↗

Public Reference Data for Megawatt-Scale Hydrogen Electrolysis - Simulated Marine Hydrokinetic Tidal Turbine

The U.S. Department of Energy and National Laboratory of the Rockies (NLR) demonstrate hydrogen electrolysis, hydrogen compression and storage, and variable hydrogen fuel cell power production using megawatt-scale equipment at NLR’s Flatirons Campus as part of the Advanced Research on Integrated Energy Systems (ARIES) initiative. This dataset is part of that effort and is intended for academic, national laboratory, industrial, and other stakeholders to plan, design, and validate models of megawatt-scale hydrogen technologies and diverse energy infrastructure. These data provide a baseline for how existing hydrogen electrolysis technologies perform when coupled with other energy technologies. This dataset contains inputs and outputs from simulations of a floating marine hydrokinetic turbine over approximately half a tidal cycle (~6.6 hours). Inflow conditions were derived from field measurements in Alaska’s Cook Inlet and represent a tidal environment in which the current speed ramps from near 0 m/s to a peak of 3 m/s and back. The original acoustic doppler current profiler dataset is publicly available on the Marine and Hydrokinetic Data Repository. In a full tidal cycle, the flow reverses and the rotor would reorient; this reversal was not modeled. In the Cook Inlet campaign , turbulence intensity was similar in both directions. Two inflow cases are included. In the first case, labeled “raw” in the files, the measured current time series was used directly in the InflowWind module of OpenFAST. Speed and direction were applied as a function of time and elevation, uniformly in the horizontal direction. With full spatial coherence, this approach captures high turbulent variability and results in pronounced power fluctuations, so it is considered a conservative, near-worst-case representation of loading. In the second case, labeled “average” in the files, a 30-minute moving average was applied to extract the slowly varying mean speed. The residual fluctuations about this mean were used to generate spatially varying, full-field turbulence inputs with TurbSim, giving a more physically realistic representation of the inflow across the rotor disk. Two random realizations were used to produce distinct inflow conditions for two OpenFAST simulations representing a two-turbine array. The same turbulence intensity is applied across the full time series, producing larger fluctuations at the start and end, where the mean speed is low. The second case is the more appropriate framework for performance and power assessment but overpredicts turbulence at lower flow speeds and underpredicts it at higher speeds. As the floating platform moves and the rotor changes its x-position, Taylor’s frozen turbulence hypothesis used by InflowWind assumes a constant rather than a time-varying mean velocity, introducing some inaccuracy in the velocity plane sampling. The turbine modeled is the 500-kW Reference Model 1, a horizontal-axis two-bladed hydrokinetic turbine on a four-column floating semisubmersible substructure . Simulations were performed using OpenFAST v4.1 with the Reference Open Source Controller (ROSCO) v2.10. All input files required to reproduce the simulations are included. The electrolyzer is a 1.25-MW proton exchange membrane type MC250 system manufactured by Nel . This unit supports up to 2.5 MW, but NLR has only a single 1.25-MW stack. The datasets report hydrogen balance-of-plant and system data, all captured at 1 Hz, including hydrogen mass production measured with an Emerson Coriolis flow meter. The system controls hydrogen production by varying direct current applied to the stack, from a maximum of 3,000 A to a minimum safe operating current of 300 A, or 10%. Because the current–voltage characteristic changes as the stack ages and efficiency degrades, the actual minimum safe operating power changes over time. The simulated tidal turbine time series data was translated from power (kilowatts) to current (amperes) using a curve fit with calibration data and sent to the electrolyzer power supply at 1-Hz. Each zip file represents a single tidal electrolysis experiment and is named: {technology}_{inflow method}_{number of 500 kW tidal turbines connected} For instance, “tidal-500kW-RM1_average_2.zip” is a 6-hour experiment using the 500-kW tidal reference model, scaled by 2x (1-MW) to better match the electrolyzer maximum of 1.25MW, fed with the 30-minute moving average current case. Each zip folder contains the following files: A .csv file of raw data. An .xlsx file explaining all the fields in the raw data. A .png plot showing the time series of hydrogen production in kilograms per hour, electrolysis power consumption, and input wave power. A .csv file combines all tidal profiles as "combined_tidal_experiments.csv." A separate experiment, “characterization_200.zip,” shows the MC250 electrolyzer steady-state response with 30-minute load steps over 5 hours and is accessible with this entry.

08 HYDROGEN↗

On the 2018 Outburst of the Accreting Millisecond X-Ray Pulsar Swift J1756.9-2508 As Seen with NICER

We report on the coherent timing analysis of the 182 Hz accreting millisecond X-ray pulsar SwiftJ1756.92508during its 2018 outburst as observed with the Neutron Star Interior Composition Explorer (NICER). Combiningour NICER observations with Rossi X-ray Timing Explorer observations of the 2007 and 2009 outbursts, we alsostudied the long-term spin and orbital evolution of this source. We find that the binary system is well describedby a constant orbital period model, with an upper limit on the orbital period derivative of Pb < 7.4 ´ 10-13 ss1.Additionally, we improve upon the source coordinates through astrometric analysis of the pulse arrival times,finding R.A.=17h56m57 18±0 08 and decl.=25°0627 8±3 5, while simultaneously measuring thelong-term spin frequency derivative as n = -7.3 ´ 10-16 Hzs1. We briefly discuss the implications of thesemeasurements in the context of the wider population of accreting millisecond pulsars. We reported on the coherent timing analysis of the 2018 outburst of Swift J1756 as observed with NICER. Consistent with analyses of the previous outbursts (Krimm et al. 2007b; Patruno et al. 2010), we find that the X-ray pulsations have energy dependent amplitudes; the fractional amplitude of the fundamental increases with energy, whereas the fractional amplitude of the harmonic shows a slight decline with energy. This energy dependent behavior is not unusual in AMXPs (Patruno & Watts 2012) and can be interpreted in terms of the thermal emission from the stellar hotspot and reprocessing in the accretion column (e.g., Gierliński et al. 2002; Ibragimov & Poutanen 2009). The pulse arrival times of the 2018 outburst are well described by a timing model consisting of a circular orbit with a constant spin frequency. The pulse phases with respect to this model do not show spurious residuals with time or orbital phase, and no evidence is found that the pulse arrival times exhibit an additional delay associated with passing through the gravitational well of the companion star (Shapiro delay). We note, however, that the expected Shapiro delay is given as (Shapiro et al. 1971) Equation (5) where Φ is the orbital phase, G is the gravitational constant, c is the speed of light, and i is the inclination. Even for the maximum allowed companion mass, ${M}_{C}=0.030\,{M}_{\odot }$ (Krimm et al. 2007b, but see Section 4.2 for more details) and an inclination of 90°, the largest delay we can expect is only 4 μs. As this time-delay is smaller than the uncertainty on our phase residuals by nearly two orders of magnitude (see Figure 1), we are not sensitive to Shapiro delays in Swift J1756. Comparing our measurements for the 2018 outburst with those of the 2007 and 2009 outbursts as observed with RXTE, we analyzed the long-term evolution of this source. We found that the binary system is consistent with having a constant orbital period and that the pulsar shows a spin frequency derivative of $\dot{\nu }=-7.3\times {10}^{-16}\,\mathrm{Hz}\,{{\rm{s}}}^{-1}$. 4.1. Spin-down Evolution The long-term spin frequency derivative measured in Swift J1756 is of the same order as the spin frequency derivatives measured in other AMXPs (Hartman et al. 2008; Patruno 2010; Riggio et al. 2011). This frequency change is most likely driven by the neutron star's loss of rotational energy. If so, then the spin-down luminosity is given as Equation (6) where I represents the neutron star moment of inertia. The long-term spin-down of a neutron star is usually assumed to be dominated by the braking torque associated with a spinning magnetic field. Assuming this mechanism is responsible for the observed spin-down in Swift J1756, we can compute the magnetic dipole moment as (Spitkovsky 2006) Equation (7) where α is the misalignment angle between the rotational and magnetic poles. Considering α = 0°–90°, we then find a magnetic field strength of $B\simeq (4\mbox{--}6)\times {10}^{8}$ G at the stellar magnetic poles. This magnetic field strength estimate is in line with those obtained for other accreting millisecond pulsars (see Mukherjee et al. 2015 and references therein). 4.2. Orbit Evolution The observed long-term binary evolution of Swift J1756 is consistent with this source having a constant orbital period and a lower limit on the evolutionary timescale of Equation (8) Binary evolution theory predicts that systems of this type evolve due to angular momentum loss through gravitational radiation (Kraft et al. 1962; Rappaport et al. 1982; Verbunt 1993). For conservative mass transfer, the binary period derivative is given by di Salvo et al. (2008), Equation (9) where MNS is the neutron star mass, $q={M}_{C}/{M}_{\mathrm{NS}}$ is the binary mass ratio, and −1/3 < n < 1 is the mass–radius index of the companion star. Depending on the source inclination, Krimm et al. (2007b) derived a companion mass of ${M}_{C}\,=0.007\mbox{--}0.022\,{M}_{\odot }$ for a neutron star mass of 1.4 ${M}_{\odot }$. For a neutron star mass of 2.2 ${M}_{\odot }$, the allowed range increased to ${M}_{C}=0.009\mbox{--}0.030\,{M}_{\odot }$. In both cases, they assumed an upper limit on the inclination of i < 85°, motivated by the fact that Swift J1756 does not show eclipses in its light curve. Accounting for the extreme cases of stellar masses and n, the binary may either be contracting or expanding. In either case, however, the rate of change is limited to $| {\dot{P}}_{b}| \lesssim 7\times {10}^{-14}$ s s−1, which is well below the upper limit obtained in this work. Although the binary evolution timescale we obtain for Swift J1756 is consistent with theory, it is worth noting that this is not generally true for low-mass X-ray binaries (see Patruno et al. 2017, for a comprehensive discussion). The AMXP SAX J1808.4–3658, in particular, has been found to evolve on a much shorter timescale, with a first derivative on the orbital period of $3.5\times {10}^{-12}$ s s−1 (Hartman et al. 2008; Patruno et al. 2012; Sanna et al. 2017a). Two models have been proposed to explain this discrepancy: highly nonconservative mass transfer due to irradiation of the companion star by the pulsar (di Salvo et al. 2008; Burderi et al. 2009), and spin–orbit coupling in the companion star (Hartman et al. 2008, 2009). While the latter depends on the companion star, and may vary from source to source, the former should operate in all AMXPs (see also Patruno 2017; Sanna et al. 2017c), including Swift J1756. The spin-down luminosity impinging on the companion star can be estimated as Equation (10) where ${\dot{E}}_{\mathrm{abl}}$ is the ablation luminosity, RL2 is the Roche lobe radius of the companion (Eggleton 1983), and a the binary separation. The irradiation fraction is $f={\dot{E}}_{\mathrm{abl}}/{\dot{E}}_{\mathrm{sd}}$, which, accounting for the range of allowed neutron star and companion masses, evaluates to f = 0.15%–0.35%. The associated mass loss for the companion is given by Equation (11) such that, assuming an efficiency of η = 100%, ${\dot{M}}_{C}\,\sim -3\times {10}^{-10}\,{M}_{\odot }$ yr−1. The effect of this mass loss on the orbital period follows through the relation (Frank et al. 2002) Equation (12) giving a period derivative due to mass loss of ${\dot{P}}_{b,\mathrm{ML}}\,=5\times {10}^{-12}$ s s−1. This value is well above our limit on the period derivative. Hence, in order for this mechanism to be consistent with our observations of Swift J1756, the efficiency at which the companion star converts the incident luminosity into mass loss must be η < 15%. This value is very different from the 40% required in SAX J1808.4–3658 (Patruno et al. 2016) and is instead in line with the <5% efficiency determined for IGR J00291+5934 (Patruno 2017). This work was supported by NASA through the NICER mission and the Astrophysics Explorers Program, and made use of data and software provided by the High Energy Astrophysics Science Archive Research Center (HEASARC). P.B. was supported by an NPP fellowship at NASA Goddard Space Flight Center. D.A. acknowledges support from the Royal Society.

Bult, Peter↗

Fluidized-Bed Gasification of Coal-Biomass-Plastics for Hydrogen Production

Coal is one of the most abundant fossil energy resources in the United States and in the world. The recoverable reserves in the United States are estimated to be about 252 billion tons – more than 350 years of supply at current rates of usage. However, the share of coal in total primary energy consumption in the US has been declining over the years. The decline of coal is mainly attributed to cheap natural gas and precipitous declines in the cost of electricity production from renewable technologies such as wind and solar. Coal can potentially be used if it is coupled with carbon-neutral feedstock such as biomass-agricultural residues, forest biomass, and forest residues. Co-gasification of coal and biomass can become a negative carbon emission technology if the carbon dioxide (CO 2 ) is captured and sequestered. Although the biomass gasification process has a lot of similarities to coal gasification, the large-scale adaptation of power production sourced from biomass has not come to fruition. The main reason is that the power production from biomass is still expensive when compared with natural gas or coal power technologies. To address the feedstock cost, one approach is to use low-cost feedstocks, such as municipal solid wastes (MSW) or plastics, for gasification. Gasification involves the partial oxidation of coal and/or biomass feedstocks to produce a combustible fuel called synthesis gas (syngas) which is composed of carbon monoxide (CO), hydrogen (H 2 ), CO 2 , methane (CH 4 ), nitrogen (N 2 ), water (H 2 O), and other compounds that might be considered as contaminants. Raw syngas from gasification must go through multiple steps to produce high-purity hydrogen. The specific steps depend upon the quality (gas composition, contaminants, and their concentration) and condition (pressure and temperature) of syngas. The long-term goal of the project was to utilize coal and plastics together with biomass to produce energy and fuels using a gasification platform while reducing greenhouse gas emissions. The main objective of this research was to examine gasification performance in a laboratory-scale fluidized-bed gasifier for hydrogen production. The specific objectives of the research were to: (i) study coal-plastic-biomass mixture flowability for consistent feeding in the gasifier; (ii) understand the gasification behavior of the mixture in steam and oxygen environments; (iii) perform thermal property characterization of ash and slag from the mixture feedstock and refractory-ash interface of the mixture under gasification conditions; and (iv) develop process models to determine the technology needed for syngas cleanup and contaminants. The study found that there was no apparent segregation when biomass, coal, and waste plastics were mixed together during feeding. Although there were differences in hydrogen production when individual feedstock were fed, the hydrogen concentration remained almost constant with various blends. Therefore, blending waste plastics with biomass and coal, which are all abundant, is a better approach for energy production. Results of the techno-economic analysis suggested that integration of advanced gasification (GTI’s R-GAS™) and syngas cleanup and conditioning technologies (RTI’s WDP and AFWGS) for clean hydrogen production resulted in substantial benefits, including significant capital cost and operating cost reductions. Advanced technologies resulted in 16% reduction in the hydrogen production cost (COH) from 2.94 $\$$/kg to 2.47 $\$$/g, with further scope for optimization and cost reduction. These advanced technologies also result in lower emissions, and improved energy efficiency.

01 COAL, LIGNITE, AND PEAT↗

Initial study on cross-section generation requirements for a PBR equilibrium core

A Serpent model of the equilibrium core HTR-PM small modular nuclear reactor in China, was developed for use in cross-section preparation studies in order to guide methods development for the Griffin reactor multiphysics application. The model includes detailed isotopics for 10 distinct pebble burnup groups in 126 core zones with unique fuel and moderator temperatures obtained from a coupled neutronics-thermal-fluids equilibrium core calculation using Griffin-Pronghorn. A sensitivity study of the fuel and moderator temperatures for various core regions was performed with the MOOSE stochastic tools. The results show that the uncertainties are, not unexpectedly, dominated by the value of the fluid temperature and that the power level, heat transfer coefficient and effective conduction to neighboring pebbles and fluid constitute, at best, second order effects. The temperature uncertainty range varies from 28 K to 57 K between the core entry and exit planes, respectively, but these values are probably higher. We still have to quantify the significance of these uncertainties in the preparation of cross-sections in future work. In addition, we verified that the effective pebble approximation used in the PEBBED and V.S.O.P. computer codes works well for the preparation of region averaged cross-sections. Nevertheless, there are some discrepancies in the cross-sections when compared to the multi-pebble model, which could affect the prediction of peak values and the depletion calculation. We conclude that is highly desirable for future studies with Griffin to be able to handle both the 'effective' pebble approximation and the multi-pebble approach for various pebble burnup groups. This enables Griffin users with the flexibility to perform higher-fidelity studies. Finally, we initiated the preparation of cross-sections for various core regions from the full core Serpent reference model. We quantified the differences in 26 group cross-sections from infinite domain models versus the full core approach. These reference cross-sections will serve to verify the double heterogeneity, self-shielding, and spectrum-correction methods in Griffin. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Three-dimensional organization of otolith-ocular reflexes in rhesus monkeys. I. Linear acceleration responses during off-vertical axis rotation

1. The dynamic properties of otolith-ocular reflexes elicited by sinusoidal linear acceleration along the three cardinal head axes were studied during off-vertical axis rotations in rhesus monkeys. As the head rotates in space at constant velocity about an off-vertical axis, otolith-ocular reflexes are elicited in response to the sinusoidally varying linear acceleration (gravity) components along the interaural, nasooccipital, or vertical head axis. Because the frequency of these sinusoidal stimuli is proportional to the velocity of rotation, rotation at low and moderately fast speeds allows the study of the mid-and low-frequency dynamics of these otolith-ocular reflexes. 2. Animals were rotated in complete darkness in the yaw, pitch, and roll planes at velocities ranging between 7.4 and 184 degrees/s. Accordingly, otolith-ocular reflexes (manifested as sinusoidal modulations in eye position and/or slow-phase eye velocity) were quantitatively studied for stimulus frequencies ranging between 0.02 and 0.51 Hz. During yaw and roll rotation, torsional, vertical, and horizontal slow-phase eye velocity was sinusoidally modulated as a function of head position. The amplitudes of these responses were symmetric for rotations in opposite directions. In contrast, mainly vertical slow-phase eye velocity was modulated during pitch rotation. This modulation was asymmetric for rotations in opposite direction. 3. Each of these response components in a given rotation plane could be associated with an otolith-ocular response vector whose sensitivity, temporal phase, and spatial orientation were estimated on the basis of the amplitude and phase of sinusoidal modulations during both directions of rotation. Based on this analysis, which was performed either for slow-phase eye velocity alone or for total eye excursion (including both slow and fast eye movements), two distinct response patterns were observed: 1) response vectors with pronounced dynamics and spatial/temporal properties that could be characterized as the low-frequency range of "translational" otolith-ocular reflexes; and 2) response vectors associated with an eye position modulation in phase with head position ("tilt" otolith-ocular reflexes). 4. The responses associated with two otolith-ocular vectors with pronounced dynamics consisted of horizontal eye movements evoked as a function of gravity along the interaural axis and vertical eye movements elicited as a function of gravity along the vertical head axis. Both responses were characterized by a slow-phase eye velocity sensitivity that increased three- to five-fold and large phase changes of approximately 100-180 degrees between 0.02 and 0.51 Hz. These dynamic properties could suggest nontraditional temporal processing in utriculoocular and sacculoocular pathways, possibly involving spatiotemporal otolith-ocular interactions. 5. The two otolith-ocular vectors associated with eye position responses in phase with head position (tilt otolith-ocular reflexes) consisted of torsional eye movements in response to gravity along the interaural axis, and vertical eye movements in response to gravity along the nasooccipital head axis. These otolith-ocular responses did not result from an otolithic effect on slow eye movements alone. Particularly at high frequencies (i.e., high speed rotations), saccades were responsible for most of the modulation of torsional and vertical eye position, which was relatively large (on average +/- 8-10 degrees/g) and remained independent of frequency. Such reflex dynamics can be simulated by a direct coupling of primary otolith afferent inputs to the oculomotor plant. (ABSTRACT TRUNCATED).

NASA Discipline Neuroscience↗

Fundamental Studies of Bifunctional Catalysts for Tandem Reactions

During the past few years of our funding from DOE Basic Energy Sciences, we have focused on the catalytic conversion of biomass-derived 5-hydroxymethyl furfural (HMF) as a platform molecule for sustainable synthesis of value-added chemicals. The combination of the diene and aldehyde functionalities in HMF enables catalytic production of acetalized HMF derivatives with diol or epoxy reactants to allow reversible synthesis of norcantharimide derivatives upon Diels-Alder reaction with maleimides. Whereas the electron-withdrawing nature of aldehyde group inhibits the reactivity of diene group in HMF to undergo Diels-Alder reactions with dienophiles, by converting the aldehyde group in HMF to an electron-donating hydroxyl group, HMF can append maleimide-based chemicals through Diels-Alder coupling. Acetalization of HMF not only produces an electron-rich diene for Diels-Alder reaction, but it also alters the reversibility of acetal formation and thereby allows for the controlled release of chemicals by hydrolysis. Therefore, we synthesized various norcantharimide derivatives from biomass-derived HMF by acetalization over an acid catalyst, Amberlyst-15, followed by Diels-Alder reaction with maleimide. The norcantharimides release the starting materials by retro Diels-Alder reaction that is triggered by acetal hydrolysis under acidic (≤pH 3) conditions. In subsequent work, we explored the synthesis and properties of functional polyurethanes and polyesters with tunable properties from biomass-derived (HMF)-Acetone-HMF (HAH) monomers. HAH can be selectively hydrogenated over Cu and Ru catalysts to produce partially-hydrogenated HAH (PHAH) and fully-hydrogenated HAH (FHAH). HAH contains functional groups, including hydroxyl, furan, enone, and ketone functionalities, that can be exploited to further tune the polymer properties. The π-electron conjugation between the enone and furan groups in HAH monomer stabilizes the furan group to prevent the uncontrolled degradation of furans during reactions, such as etherification. Therefore, HAH is a renewable monomer that can be used to synthesize polymers, having high molecular weight, symmetric functionalities, an inexpensive production price, and being derived from renewable resources without competition with food resources. We demonstrated the synthesis of functional polyurethanes and a renewable polyester from HAH-derived monomers, and 4,4’-methylenebis(phenyl isocyanate) (MDI). We showed that it is essential to be able to selective hydrogenate C=C double bonds in HAH to be able to achieve effective Diels Alder reactions of the furan ring. Therefore, we studied the hydrogenation at temperatures from 313 – 393 K of HAH over Pd, Ru, and Cu based catalysts. HAH was selectively hydrogenated to produce partially-hydrogenated monomers (PHAH) over Cu and Ru catalysts and to fully-hydrogenated HAH monomers (FHAH) over the Ru catalyst. Pd based catalysts yielded a mixture of partially and fully hydrogenated monomers. Reaction kinetics models were employed to quantify the kinetic behavior for hydrogenation over Ru, Cu, and Pd catalysts. A 5-step pathway exhibited over Pd and Ru catalysts consists of both series and parallel reaction steps, where HAH is both converted to fully hydrogenated products sequentially via series reactions of partially hydrogenated intermediates, as well as converted directly in parallel reactions to form the fully hydrogenated products. In contrast, a 3-step pathway over the Cu catalyst consists only of the consecutive reaction steps, where the final product was formed via series reactions of intermediate products. Additionally, reaction over the Cu catalyst did not hydrogenate the furan rings of the HAH molecule and yielded a different final product than those hydrogenation over Pd and Ru catalysts. Using the results from our detailed reaction kinetics studies, we developed universal conditions for the maximum production of the various hydrogenated products for both batch and plug flow systems. In subsequent work, we employed reaction schemes to optimize the yields of products from selective hydrogenations of HAH in isopropanol solvent and in the presence of liquid water. Reaction schemes consisting of 7, 9, and 11 steps were examined to describe the rates of formation of the observed products and reaction intermediates for hydrogenation of HAH over Ru and Pd catalysts, and a 3-step scheme was studied over Cu catalysts. Rate constants and activation energies were calculated using these reaction schemes, and we then apply these reaction schemes to explore the effects of water addition on the hydrogenation pathways. The effects of water addition to isopropanol (IPA) solvents on the hydrogenation of HAH were markedly different over Pd, Ru, and Cu catalysts. Over the Pd catalyst, the addition of water to IPA increased hydrogenation rates and promoted hydrogenation of furan rings. The addition of water to IPA yielded significant carbon losses over the Ru catalyst, and slowed hydrogenation steps over Cu, while significantly inhibiting hydrogenation of the ketone group. This behavior opened routes toward increased production rates of PHAH=O (a partially hydrogenated form of HAH containing a C=O bond), a product in which the diene groups of the furan rings were not hydrogenated. Addition of water also allowed increased feed concentrations of HAH that were previously not possible in pure IPA solvents.

09 BIOMASS FUELS↗

Influence of Nucleation Mechanisms on the Radiative Properties of Deep Convective Clouds and Subvisible Cirrus in CRYSTAL/FACE

During the past few years we have conducted work on several different topics, as reflected by our publications. As one of the Co-Project scientists for The Cirrus Regional Study of Tropical Anvils and Cirrus Layers - Florida Area Cirrus Experiment (CRYSTAL FACE) we worked to help design the mission and then conduct it in the field. Another major activity during the past two years has been to pull together various groups to formulate plans for follow on missions to CRYSTAL FACE. We organized a workshop at the University of Colorado during the summer of 2003 to assess the best locations for future missions. Working with a group of about 10 scientists from around the country we prepared a science-planning document (Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) that outlined the rationale, locations, strategy to accomplish the goals, and possible payloads for a set of three tropical missions. We also prepared background materials for various NRAs being prepared at NASA Headquarters for missions in Costa Rica, Darwin and Guam. In conjunction with the group at NASA Ames we have helped build a new numerical model for deep convection and have applied that model to simulate the CRYSTAL data. Our goal in particular has been to better understand how convection distributes water vapor isotopes. CRYSTAL observations of water isotopes are very different from those suggested by previous workers who assumed the isotopes would obey Rayleigh fractionation. The water isotope study has several implications. First it is a check on the realism of the deep convection model. Second, the isotopes are a measure of the precipitation removal in the atmosphere. Hence they provide a constraint on a parameter that is difficult to otherwise measure. Finally it has been suggested that isotopes may be the key to unraveling the water transport into the stratosphere and upper troposphere. Such transport is critical both for the radiation balance and for stratospheric chemistry. Ours is the first model that is able to treat this transport. Our initial results have just been submitted to Geophys. Res. Lett (Smith et al., 2005). Essentially we are able to explain the vertical profiles of isotopes in the tropical tropopause transition layer. We are also able to account for stratospheric humidity and isotope abundances with this model. We have also been heavily involved in trying to improve our understanding of nitric acid condensation on ice. Gao et al (2004) have shown that water supersaturations above ice occur when the atmosphere is supersaturated with respect to nitric acid trihydrate. As one of the co-authors of that work, we suggested the mechanism that may explain why this is occurring. Essentially, ice does not like to grow near unit supersaturation, but does so because the water molecules can find sites on the ice surface to attach themselves to before they fly off the ice surface. This phenomena was well known in the 1960s when it was a source of debate about whether condensation and evaporation coefficients for ice would be the same. Evaporation does not require any molecular orientation, while condensation does, so it was possible that the coefficients would differ. They don't differ because the water molecules rapidly move across the surface and find places to attach. Nitric acid may be occupying these preferred sites and therefore the water molecules can't find a desirable place to attach. We anticipate that this research will be the subject of laboratory work during the coming few years. Another possibility that has been suggested is that cubic ice is forming in clouds. We have measured the vapor pressure of cubic ice, and plan to publish that result in the next few months. We have also been working on additional aspects of the condensation of nitric acid on ice. With Y. Kondo we studied the condensation of NOy on ice using the SOLVE data. Gamblin et al. have continued this work. The CRYSTAL NOy and HNO, groups have shown th their data can be fit using standard Langmuir isotherms as suggested in some, but not all, laboratory studies. We have found in the SOLVE data set that this is not the case. Moreover some laboratory studies show there are important kinetic effects that may be occurring in the atmosphere limiting the transfer of nitric acid to the ice. The SOLVE data seem consistent with these studies. We are currently re-analyzing the CRYSTAL data to look for these kinetic effects. There are a number of implications of these studies. One of the more interesting is that the nitric acid coating on ice can be used as a cloud clock to determine how long the cloud parcel has been in existence. We have also been involved with several laboratory studies. We have worked to improve the database on ice optical constants, which are critical for remote sensing. We have also studied the ways in which ice nucleates on clays. We suspect now that the standard theories used for depositional ice nucleation are completely incorrect. Further work will be needed to develop a new theory.

Toon, Owen B.↗

A Kinetic and Product Study of the Cl + HO2 Reaction

Absolute rate data and product branching ratios for the reactions Cl + HO2 to HCl + O2 (k1a) and Cl + HO2 to OH + ClO (k1b) have been measured from 226 to 336 K at a total pressure of 1 Torr of helium using the discharge flow resonance fluorescence technique coupled with infrared diode laser spectroscopy. For kinetic measurements, pseudo-first-order conditions were used with both reagents in excess in separate experiments. HO2 was produced by two methods: through the termolecular reaction of H atoms with O2 and also by the reaction of F atoms with H2O2. Cl atoms were produced by a microwave discharge of Cl2 in He. HO2 radicals were converted to OH radicals prior to detection by resonance fluorescence at 308 nm. Cl atoms were detected directly at 138 nm also by resonance fluorescence. Measurement of the consumption of HO2 in excess Cl yielded k1a and measurement of the consumption of Cl in excess HO2 yielded the total rate coefficient, k1. Values of k1a and k1 derived from kinetic experiments expressed in Arrhenius form are (1.6 +/- 0.2) x 10-11 exp[(249 +/- 34)/T] and (2.8 +/- 0.1) x 10-11 exp[(123 +/- 15)/T] cm3 molecule-1 s-1, respectively. As the expression for k1 is only weakly temperature dependent, we report a temperature-independent value of k1 = (4.5 +/- 0.4) x 10-11 cm3 molecule-1 s-1. Additionally, an Arrhenius expression for k1b can also be derived: k1b = (7.7 +/- 0.8) x 10-11 exp[-(708 +/- 29)/T] cm3 molecule-1 s-1. These expressions for k1a and k1b are valid for 226 K T 336 and 256 K T 296 K, respectively. The cited errors are at the level of a single standard deviation. For the product measurements, an excess of Cl was added to known concentrations of HO2 and the reaction was allowed to reach completion. HCl product concentrations were determined by IR absorption yielding the ratio k1a/k1 over the temperature range 236 K T 296 K. OH product concentrations were determined by resonance fluorescence giving rise to the ratio k1b/k1 over the temperature range 226 K T 336 K. Both of these ratios were subsequently converted to absolute numbers. Values of k1a and k1b from the product experiments expressed in Arrhenius form are (1.5 +/- 0.1) x 10-11 exp[(222 +/- 17)/T] and (10.6 +/- 1.5) x 10-11 exp[-(733 +/- 41)/T] cm3 molecule-1 s-1, respectively. These expressions for k1a and k1b are valid for 256 K T 296 and 226 K T 336 K, respectively. A combination of the kinetic and product data results in the following Arrhenius expressions for k1a and k1b of (1.4 +/- 0.3) x 10-11 exp[(269 +/- 58)/T] and (12.7 +/- 4.1) x 10-11 exp[-(801 +/- 94)/T] cm3 molecule-1 s-1, respectively. Numerical simulations were used to check for interferences from secondary chemistry in both the kinetic and product experiments and also to quantify the losses incurred during the conversion process HO2 to OH for detection purposes.

rate constants↗