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Mechanism and Kinetics of Ethanol–Acetaldehyde Conversion to 1,3-Butadiene over Isolated Lewis Acid La Sites in Silanol Nests in Dealuminated Beta Zeolite

Biomass-derived ethanol (EtOH) and acetaldehyde (AcH) conversion to 1,3-butadiene (1,3-BD) is an alternative process for 1,3-BD production. The present investigation reports the preparation and characterization of isolated La sites introduced into the silanol nests in DeAlBEA as well as detailed studies of the mechanism and kinetics for the conversion of an EtOH-AcH mixture to 1,3-BD. La sites supported on DeAlBEA are found to be present as (≡SiO) 2 La-OH groups that are H-bonded with adjacent Si-OH groups, possessing high C-C coupling activity and stability, superior to state-of-the-art Y-DeAlBEA. La sites supported on silica (La-SiO 2 ) with a similar chemical structure but no H-bonding interaction with Si-OH groups were prepared for comparison. Lewis acid La sites promote AcH aldol condensation, and the activity of such sites is nearly identical for both La-DeAlBEA and La-SiO 2 . Further, the rate of C 4 product formation increases by a factor of 4.8 upon addition of EtOH to the feed of AcH over La-DeAlBEA, whereas that over La/SiO 2 remains unchanged. Investigation of the mechanism and kinetics of AcH aldol condensation and EtOH-AcH conversion to 1,3-BD revealed two C-C bond forming pathways-AcH aldol condensation by Lewis acid La sites and direct coupling of EtOH-AcH over H-bonded (≡SiO) 2 La-OH···HO-Si≡ sites. This study provides important information about the role of the local environment of isolated Lewis acid sites and their effects on the direct coupling of EtOH and AcH to form 1,3-BD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Impacts of Rotational Mixing on the Precipitation Simulated by a Convection Permitting Model

With increased availability of computational resources, regional and global scale convection-permitting model (CPM, Δx ~ 1–10 km) simulations are becoming more common. CPMs have improved accuracy in their representation of deep convection and mesoscale convective systems (MCSs) compared to coarser resolution models. However, CPMs still exhibit convective cloud and precipitation biases relative to observations, notably a lesser frequency of light precipitation rates and greater frequency of heavy precipitation rates. In this work we hypothesize that these CPM biases are related to under-resolved mixing between convective updrafts and their surrounding environment. To test this hypothesis, we introduce a parameterization to the Weather Research and Forecasting model (WRF) that adds a small angular rotation of the grid-scale flow about the axis perpendicular to the plane of convective drafts. This rotated flow is then allowed to alter advection of moisture and hydrometeors. The effects of such mixing on precipitation characteristics are evaluated in month-long 4-km grid spacing simulations over the Amazon. The enhanced mixing transports moisture and condensate from convective cores to other areas including downdrafts. This increases the frequency of low-precipitable water and light precipitation. It also decreases the frequency of intense precipitation from isolated deep convection and MCSs, increases cloud top temperatures, reduces radar echo-top heights, and increases overall precipitation by altering the relationship of precipitation with precipitable water, in better agreement with observations. The results suggest when optimized using multiple observations, such an approach may provide a path toward more accurate representation of convection and precipitation statistics in convection-permitting simulations.

54 ENVIRONMENTAL SCIENCES↗

Local site behavior of the 5$d$ and 4$f$ ions in the frustrated pyrochlore Ho 2 Os 2 O 7

The pyrochlore osmate Ho 2 Os 2 O 7 is a candidate material for a fragile J=0 local singlet ground state, however little is known regarding the single-ion behavior of either the Os or Ho ions. To address this we present polarized neutron powder diffraction (PNPD) and resonant inelastic x-ray scattering (RIXS) measurements that separately probe the local site behavior of the Os and Ho ions. The PNPD results are dominated by Ho 3+ scattering and the analysis reveals local site susceptibility behavior consistent with spin ice materials. Complimentary unpolarized neutron powder diffraction show an ordered spin ice ground state in an applied magnetic field. To isolate the Os 4+ single-ion behavior we present resonant inelastic x-ray scattering (RIXS) measurements at the osmium L-edge. Analysis of the RIXS spectra parameterize the spin-orbit coupling (0.35 eV), Hund’s coupling (0.27 eV) and trigonal distortion (-0.17 eV). Here, the results are considered within the context of a J=0 model and possible departures from this through structural distortions, excitonic interactions and 5d-4f interactions between the Os ion and the surrounding Ho lattice. The experimental methodology employed highlights the complimentary information available in rare earth based 5d pyrochlores from distinct neutron and x-ray scattering techniques that allow for the isolation and determination of the behavior of the different ions.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Pluto and Charon Seen with the New Horizons Spacecraft

After nearly a decade en route, New Horizons flew through the Pluto system in July 2015. The encounter hemisphere of Pluto shows ongoing surface geological activity centered on a vast basin (Sputnik Planum [SP]*) containing a thick layer of volatile ices with a crater retention age no greater than approximately 10 Ma. Surrounding terrains show active glacial flow, apparent transport and rotation of large buoyant water-ice crustal blocks, and pitting, likely by sublimation erosion and/or collapse. Also seen are constructional mounds with central depressions, and ridges with complex bladed textures. Pluto has ancient cratered terrains up to approximately 4 Ga old that are fractured and mantled, and perhaps eroded by glacial processes. Charon does not appear to be currently active, but experienced major tectonism and resurfacing nearly 4 Ga ago. Imaging spectrometer observations of Pluto reveal the encounter hemisphere to be dominated by volatile ices of N2, CO, and CH4, along with non-volatile components that include H2O and tholins. The most volatile of Pluto's ices (N2 and CO) are especially prevalent in the western half of Tombaugh Regio (TR), and the strikingly flat Sputnik Planum basin, which lies a few km below surrounding elevations. The high mobility of N2 and CO ices enables SP's surface to refresh itself sufficiently rapidly that no impact craters are seen there. This likely occurs through a combination of solid state convective overturning and sublimation/ condensation that produces regular patterns of pits and ridges on scales of 102 to 103 m. In many areas, CH4 appears to favor topographically high regions. Its propensity to condense on ridges could play a role in forming the bladed terrain seen in Tartarus Dorsa. H2O can be discerned across much of Cthulhu Regio, and also in a few isolated spots. In many regions, H2O ice is associated with reddish tholin coloration. Pluto's atmosphere was probed with the radio science experiment (REX) and the Alice UV spectrometer, as well as imaging at high phase angles. The surface pressure, due mostly to N2, is approximately 11 microbars. Extensive multiple haze layers are seen in the images. Alice has detected hydrocarbons in addition to CH4 in the atmosphere. Since both are inert, H2O ice and tholin could have similar geological behaviors on Pluto, possibly including aeolian transport or mobilization by volatile ice glaciation. While Pluto's H2O ice is sculpted and at least partially veiled by more volatile ices, Charon's heavily cratered H2O ice is exposed globally. H2O ice spectral bands characteristic of crystalline ice are seen everywhere on the encounter hemisphere. Charon's north polar region is strikingly red, possibly the result of the unique thermal environment of Charon's poles, which become exceptionally cold during the long, dark winters. Extremely cold regions on Charon' could cold trap gases expanding outward from Pluto as ices, and thereby subject them to rapid radiolytic processing. Charon also exhibits a weak NH3 absorption band over most or all of its surface, with small local concentrations. Detailed results of the radio science, small satellite, particles and plasma, and atmosphere investigations are in press.

Pluto↗

Emergence of Topologically Nontrivial Spin-Polarized States in a Segmented Linear Chain

The synthesis of new materials with novel or useful properties is one of the most important drivers in the fields of condensed matter physics and materials science. Discoveries of this kind are especially significant when they point to promising future basic research and applications. Van der Waals bonded materials comprised of lower-dimensional building blocks have been shown to exhibit emergent properties when isolated in an atomically thin form. Here, we report the discovery of a transition metal chalcogenide in a heretofore unknown segmented linear chain form, where basic building blocks each consisting of two hafnium atoms and nine tellurium atoms (Hf 2 Te 9 ) are van der Waals bonded end-to-end. First-principle calculations based on density functional theory reveal striking crystal-symmetry-related features in the electronic structure of the segmented chain, including giant spin splitting and nontrivial topological phases of selected energy band states. In this work, atomic-resolution scanning transmission electron microscopy reveals single segmented Hf 2 Te 9 chains isolated within the hollow cores of carbon nanotubes, with a structure consistent with theoretical predictions. Van der Waals-bonded segmented linear chain transition metal chalcogenide materials could open up new opportunities in low-dimensional, gate-tunable, magnetic and topological crystalline systems.

36 MATERIALS SCIENCE↗

Rapid growth of anthropogenic organic nanoparticles greatly alters cloud life cycle in the Amazon rainforest

Aerosol-cloud interactions remain uncertain in assessing climate change. While anthropogenic activities produce copious aerosol nanoparticles smaller than 10 nanometers, they are too small to act as efficient cloud condensation nuclei (CCN). The mechanisms responsible for particle growth to CCN-relevant sizes are poorly understood. Here, we present aircraft observations of rapid growth of anthropogenic nanoparticles downwind of an isolated metropolis in the Amazon rainforest. Model analysis reveals that the sustained particle growth to CCN sizes is predominantly caused by particle-phase diffusion-limited partitioning of semivolatile oxidation products of biogenic hydrocarbons. Cloud-resolving numerical simulations show that the enhanced CCN concentrations in the urban plume substantially alter the formation of shallow convective clouds, suppress precipitation, and enhance the transition to deep convective clouds. The proposed nanoparticle growth mechanism, expressly enabled by the abundantly formed semivolatile organics, suggests an appreciable impact of anthropogenic aerosols on cloud life cycle in previously unpolluted forests of the world.

54 ENVIRONMENTAL SCIENCES↗

Chapter 13. Atmospheric Dynamics and Meteorology

Titan, after Venus, is the second example in the solar system of an atmosphere with a global cyclostrophic circulation, but in this case a circulation that has a strong seasonal modulation in the middle atmosphere. Direct measurement of Titan's winds, particularly observations tracking the Huygens probe at 10 deg S, indicate that the zonal winds are mostly in the sense of the satellite's rotation. They generally increase with altitude and become cyclostrophic near 35 km above the surface. An exception to this is a sharp minimum centered near 75 km, where the wind velocity decreases to nearly zero. Zonal winds derived from temperatures retrieved from Cassini orbiter measurements, using the thermal wind equation, indicate a strong winter circumpolar vortex, with maximum winds of 190 m/s at mid northern latitudes near 300 km. Above this level, the vortex decays. Curiously, the stratospheric zonal winds and temperatures in both hemispheres are symmetric about a pole that is offset from the surface pole by about 4 deg. The cause of this is not well understood, but it may reflect the response of a cyclostrophic circulation to the onset between the equator, where the distance to the rotation axis is greatest, and the seasonally varying subsolar latitude. The mean meridional circulation can be inferred from the temperature field and the meridional distribution of organic molecules and condensates and hazes. Both the warm temperatures near 400 km and the enhanced concentration of several organic molecules suggest subsidence in the north polar region during winter and early spring. Stratospheric condensates are localized at high northern latitudes, with a sharp cut-off near 50 deg N. Titan's winter polar vortex appears to share many of the same characteristics of isolating high and low-latitude air masses as do the winter polar vortices on Earth that envelop the ozone holes. Global mapping of temperatures, winds, and composition in the troposphere, by contrast, is incomplete. The few suitable discrete clouds that have been found for tracking indicate smaller velocities than aloft, consistent: with the Huygens measurements, Along the descent trajectory, the Huygens measurements indicate eastward zonal winds down to 7 km, where they shift westward, and then eastward again below 1 km dawn to the surface. The low-latitude dune fields seen in Cassini RADAR images have been interpreted as longitudinal dunes occurring in a mean eastward zonal wind. This is not like Earth, where the low-latitude winds are westward above the surface. Because the net zonal-mean time-averaged torque exerted by the surface on the atmosphere should vanish, there must be westward flow over part of the surface; the question is where and when. The meridional contrast in tropospheric temperatures deduced from radio occultations at low, mid, and high latitudes. is small, approximately 5 K at the tropopause and approximately 3 K at the surface. This implies efficient heat transport, probably by axisymmetric meridional circulations. The effect of the methane "hydrological" cycle on the atmospheric circulation is not well constrained by existing measurements, Understanding the mature of the surface-atmosphere coupling will be critical to elucidating the atmospheric transports of momentum, heat, and volatiles.

Flasar, F. M.↗

Towards an Era of Low-Temperature Integral Critical Experiments: Surrogate Testing of Low-Temperature TEX Configurations

United States and IAEA regulations for the transportation of radioactive materials require that fissile materials must be subcritical under expected ambient temperatures ranging from -40°C to 38°C. While historical experiments have been conducted at room and elevated temperatures, no criticality integral benchmarks exist for temperatures below room temperature. The Low-Temperature Thermal Epithermal eXperiments (LT-TEX) aim to provide benchmark evaluations down to -40°C. The LT-TEX design incorporates stacked HEU plates interspersed with varying thicknesses of polyethylene disks to provide varying levels of moderation, with five configurations at 20°C having already been benchmarked. A novel vacuum/cryogenic chamber was fabricated to contain the LT-TEX configurations in a thermally isolated environment and cool it to -40°C. Prior to testing with fissile materials, testing with surrogate fuel plates was performed to characterize the thermal properties of the system, ensure no condensation forms on the stack, and to test that the uranium plates would not warp, or fracture during the thermal cycling. Surrogate testing has characterized the cryogenic chamber and verified its viability to perform the benchmark experiments, allowing for the next steps in the LT-TEX experimental campaign. The results of the surrogate testing are discussed and compared to heat transfer calculations performed as part of the experiment design process, to establish confidence in the thermal behavior of the system.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Bridging the Transuranics with Uranium(IV) Sulfate Aqueous Species and Solid Phases

Isolating isomorphic compounds of tetravalent actinides (i.e., Th IV , U IV , Np IV , and Pu IV ) improve our understanding of the bonding behavior across the series, in addition to their relationship with tetravalent transition metals (Zr and Hf) and lanthanides (Ce). Similarities between these tetravalent metals are particularly illuminated in their hydrolysis and condensation behavior in aqueous systems, leading to polynuclear clusters typified by the hexamer [M IV 6 O 4 (OH) 4 ] 12+ building block. Prior studies have shown the predominance and coexistence of smaller species for Th IV (monomers, dimers, and hexamers) and larger species for U IV , Np IV , and Pu IV (including 38-mers and 70-mers). We show here that aqueous uranium(IV) sulfate also displays behavior similar to that of Th IV (and Zr IV ) in its isolated solidphase and solution speciation. Two single-crystal X-ray structures are described: a dihydroxide-bridged dimer (U 2 ) formulated as U 2 (OH) 2 (SO 4 ) 3 (H 2 O) 4 and a monomer-linked hexamer framework (U-U 6 ) as (U(H 2 O) 3.5 ) 2 U 6 O 4 (OH) 4 (SO 4 ) 10 (H 2 O) 9 . These structures are similar to those previously described for ThIV. Moreover, cocrystallization of monomer and dimer and of dimer and monomer–hexamer phases for both Th IV (prior) and U IV (current) indicates the coexistence of these species in solution. Because it was not possible to effectively study the sulfate-rich solutions via X-ray scattering from which U 2 and U-U 6 crystallized, we provide a parallel solution speciation study in low sulfate conditions, as a function of the pH. Raman spectroscopy, UV–vis spectroscopy, and small-angle X-ray scattering of these show decreasing sulfate binding, increased hydrolysis, increased species size, and increased complexity, with increasing pH. Furthermore, this study describes a bridge across the first half the actinide series, highlighting U IV similarities to Th IV , in addition to the previously known similarities to the transuranic elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Integrating adaptive learning with post hoc model explanation and symbolic regression to build interpretable surrogate models

Abstract We develop a materials informatics workflow to build an interpretable surrogate model for micromagnetic simulations. Our goal is to predict the energy barrier of a moving isolated skyrmion in rare-earth-free $$\hbox {Mn}_4$$ Mn 4 N. Our approach integrates adaptive learning with post hoc model explanation and symbolic regression methods. We discuss an unexplored acquisition function (information condensing active learning) within the adaptive learning loop and compare it with the known standard deviation function for efficient navigation of the search space. Model-agnostic post hoc explanation techniques then uncover trends learned by the trained model, which we then leverage to constrain the expressions used for symbolic regression. Graphical abstract

Biswas, Ankita↗

The seven ages of a planet

On the basis of almost universally held assumptions concerning the formation of the planets and the isolation of the solar system from outside influences it follows rather plausibly that all terrestrial planets pass in principle through seven stages. The processes involved include the solidification of grains from gas in the condensation stage, planetesimal interactions, and formation processes. Vigorous convection processes lead to the gravitational separation of iron and the outgassing of oceans. Other stages are related to plate tectonics and terminal volcanism. The ultimate stage of quiescence is characterized by a thick lithosphere and no volcanism.

Kaula, W. M.↗

Model-Based Diagnostics for Propellant Loading Systems

The loading of spacecraft propellants is a complex, risky operation. Therefore, diagnostic solutions are necessary to quickly identify when a fault occurs, so that recovery actions can be taken or an abort procedure can be initiated. Model-based diagnosis solutions, established using an in-depth analysis and understanding of the underlying physical processes, offer the advanced capability to quickly detect and isolate faults, identify their severity, and predict their effects on system performance. We develop a physics-based model of a cryogenic propellant loading system, which describes the complex dynamics of liquid hydrogen filling from a storage tank to an external vehicle tank, as well as the influence of different faults on this process. The model takes into account the main physical processes such as highly nonequilibrium condensation and evaporation of the hydrogen vapor, pressurization, and also the dynamics of liquid hydrogen and vapor flows inside the system in the presence of helium gas. Since the model incorporates multiple faults in the system, it provides a suitable framework for model-based diagnostics and prognostics algorithms. Using this model, we analyze the effects of faults on the system, derive symbolic fault signatures for the purposes of fault isolation, and perform fault identification using a particle filter approach. We demonstrate the detection, isolation, and identification of a number of faults using simulation-based experiments.

Daigle, Matthew John↗

Microbiological Contamination of Spacecraft

The International Space Station (ISS) Phase1 Program resulted in seven US astronauts residing aboard the Russian Space Station Mir between March 1995 and May 1998. Collaboration between U.S. and Russian scientists consisted of collection and analyses of samples from the crewmembers and the Mir and Shuttle environments before, during, and after missions that lasted from 75 to 209 days in duration. The effects of long-duration space flight on the microbial characteristics of closed life support systems and the interactions of microbes with the spacecraft environment and crewmembers were investigated. Air samples were collected using a Russian or U.S.-supplied sampler (SAS, RCS, or Burkard,) while surface samples were collected using contact slides (Hycon) or swabs. Mir recycled condensate and stored potable water sources were analyzed using the U.S.-supplied Water Experiment Kit. In-flight analysis consisted of enumeration of levels of bacteria and fungi. Amounts of microorganisms seen in the air and on surfaces were mostly within acceptability lin1its; observed temporal fluctuations in levels of microbes probably reflect changes in environmental conditions (e.g., humidity). All Mir galley hot water samples were within the standards set for Mir and the ISS. Microbial isolates were returned to Earth for identification of bacterial and fungal isolates. Crew samples (nose, throat, skin, urine, and feces) were analyzed using methods approved for the medical evaluations of Shuttle flight crews. No significant changes in crew microbiota were found during space flight or upon return relative to preflight results. Dissemination of microbes between the crew and environment was demonstrated by D A fingerprinting. Some biodegradation of spacecraft materials was observed. Accumulation of condensate allowed for the recovery of a wide range of bacteria and fungi as well as some protozoa and dust mites.

Pierson, D. L.↗

A novel mineral-acid free biphasic deep eutectic solvent/γ-valerolactone system for furfural production and boosting the enzymatic hydrolysis of lignocellulosic biomass

The failure of hemicellulose valorization in a deep eutectic solvent (DES) pretreatment has become a bottleneck that challenges its further development. Here, to address this issue, this study developed a DES/GVL (γ-valerolactone) biphasic system for effective hemicellulose-furfural conversion, enhanced cellulose saccharification and lignin isolation. The results indicated that the biphasic system could significantly improve the lignin removal (as high as 89.1%), 86.0% higher than the monophasic DES, accompanied by ~100% hemicellulose degradation. Notably, the GVL in the biphasic solvent restricted the condensation of hemicellulose degradation products, which as a result generated large amount of furfural in the pretreatment liquid with a yield of 68.6%. With the removal of hemicellulose and lignin, cellulose enzymatic hydrolysis yield was boosted and reached near 100%. This study highlighted that the novel DES/GVL is capable of fractionating the biomass and benefiting their individual utilization, which could provide a new biorefinery configuration for a DES pretreatment.

09 BIOMASS FUELS↗

Optimizing the surface distribution of acid sites for cooperative catalysis in condensation reactions promoted by water

Addition of small amounts of water to the organic solvent may result in different promoting or inhibiting effects in aldol condensation reactions depending on the distribution of active sites on the surface. In a combination of liquid-phase catalytic activity measurements, spectroscopies and theoretical calculations, we have shown that water clusters around the acid site can form bridges with a ketone molecule located close to the activated carbonyl, on another site. When the distance between the two acid sites is greater than a distance corresponding to about 2 water molecules, the efficiency of the bond polarization of the ketone by a remotely located acid site decreases significantly, and the presence of water no longer promotes the reaction. Furthermore, this work provides a quantitative assessment of how solvent molecules can bridge isolated active sites to enable cooperative catalysis, which offers an additional dimension for engineering catalysis at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Low-chromophore lignin isolation from natural biomass with polyol-based deep eutectic solvents

When attempting to obtain light-color lignin from lignocellulosic biomass or industrial lignin, the available options based on chemical or morphological modification suffer from low yield, high cost, and lack of availability at the required scales. In this study, we adopted a polyhydric-alcohol-based deep eutectic solvent (PA-DES) to directly extract light-color lignin from natural biomass, which is even whiter than native cellulolytic enzyme lignin (CEL). The isolated lignin possessed a high recovery yield (97.36%), regular micro-spherical morphology, enriched β-ether linkage of 58/100Ar, low phenolic hydroxyl content of 1.25 mmol g -1 , minimal carbonyl content of 0.70 mmol g -1 , and less condensed structures, thus yielding a lower content of chromophores. Further, this lignin showed excellent sunscreen effects, which could enhance the SPF of a commercial sunscreen from 15 to 40 with only 5 wt% addition. This study can provide essential guidance for the scale-up production of light-color lignin and obtaining near-complete digestible cellulose for further saccharification.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Acoustic isolation vessel for measurement of the background noise in microphones

An acoustic isolation vessel has been developed to measure the background noise in microphones. The test microphone is installed in an inner vessel, which is suspended within an outer vessel, and the intervening air space is evacuated to a high vacuum. An analytical expression for the transmission coefficient is derived, based on a five-media model, and compared to experiment. At an isolation vacuum of 5 x 10 exp -6 Torr the experimental transmission coefficient was found to be lower than -155 dB at frequencies ranging from 40 to 1200 Hz. Measurements of the A-weighted noise levels of commercial condenser microphones of four different sizes show good agreement with published values.

Ngo, Kim C. T.↗

SRF Levitation and Trapping of Nanoparticles Experiment

The levitation and trapping of micro particles using lasers is not a new accomplishment and has been applied in containerless processing and spectroscopy of microparticles. Recent developments in the field of optomechanics have achieved levitating nanoparticles such that quantum phenomena was observed which would have relevance in quantum science and technology. This two-year project sought to levitate and trap mesoscopic particles using radio frequency (RF) fields in a resonating superconducting RF (SRF) cavity. By exploiting the intrinsic characteristics of an SRF resonating cavity, the project was to explore overcoming a major limit faced by current laser trapping techniques. The goal was to establish a foundation to enable the observation of quantum phenomena of an isolated mechanical oscillator interacting with microwave fields. If successful the experiment could establish its ground-breaking relevance to quantum information science and technology.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗