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At least 73 records · Page 4

Nanoscale Etching and Indentation of Silicon Surfaces with Carbon Nanotubes

The possibility of nanolithography of silicon and germanium surfaces with bare carbon nanotube tips of scanning probe microscopy devices is considered with large scale classical molecular dynamics (MD) simulations employing Tersoff's reactive many-body potential for heteroatomic C/Si/Ge system. Lithography plays a key role in semiconductor manufacturing, and it is expected that future molecular and quantum electronic devices will be fabricated with nanolithographic and nanodeposition techniques. Carbon nanotubes, rolled up sheets of graphene made of carbon, are excellent candidates for use in nanolithography because they are extremely strong along axial direction and yet extremely elastic along radial direction. In the simulations, the interaction of a carbon nanotube tip with silicon surfaces is explored in two regimes. In the first scenario, the nanotubes barely touch the surface, while in the second they are pushed into the surface to make "nano holes". The first - gentle scenario mimics the nanotube-surface chemical reaction induced by the vertical mechanical manipulation of the nanotube. The second -digging - scenario intends to study the indentation profiles. The following results are reported in the two cases. In the first regime, depending on the surface impact site, two major outcomes outcomes are the selective removal of either a single surface atom or a surface dimer off the silicon surface. In the second regime, the indentation of a silicon substrate by the nanotube is observed. Upon the nanotube withdrawal, several surface silicon atoms are adsorbed at the tip of the nanotube causing significant rearrangements of atoms comprising the surface layer of the silicon substrate. The results are explained in terms of relative strength of C-C, C-Si, and Si-Si bonds. The proposed method is very robust and does not require applied voltage between the nanotube tips and the surface. The implications of the reported controllable etching and hole-creating for nanolithography on silicon are discussed in detail.

Dzegilenko, Fedor N.↗

Demonstration of a 600 Watt Hybrid Iodine-Xenon Electric Propulsion System

This paper reviews recent iodine compatible electric propulsion technologies evaluated at the NASA Glenn Research Center. The work culminated in a 1,174-hour hybrid iodine-xenon propulsion system durability demonstration (iodine fed thruster with xenon fed cathode). The test demonstrated that (i) a Hall-effect thruster operates with nearly identical performance whether employing iodine or xenon propellant, (ii) careful selection of propulsion system materials and coatings can result in durable iodine-compatible hardware, and (iii) implementation of appropriate facility improvements and procedures can limit negative impacts of iodine on test hardware and ground support equipment. The work was motivated by advancements in capability of very dense small-spacecraft (<500 kg), but spacecraft still lacking very dense in-space propulsion to provide the large delta-v capabilities (3 to 10 km/s) required for many high-value NASA exploration and science missions. Volume limitations of small-spacecraft not only require dense propulsion systems, but more so dense propellants. NASA identifies xenon and iodine as having both favorable storage densities and propulsive properties to enable many NASA small-spacecraft mission scenarios. While xenon is inert and well-proven in spaceflight applications, iodine has triple the storage density of xenon and stores at low pressures, permitting use of conformal tank designs. Unlike xenon, iodine does raise concerns related to its reactivity with most materials, potential spacecraft-propellant interactions, impact on ground test facilities, and challenges to acceptance test iodine propulsion systems prior to flight. This work begins to address these challenges. This work was conducted under the Advanced In-Space Propulsion (AISP) project funded through the Game Changing Development (GCD) program within NASA's Science Technology Mission Directorate (STMD).

Benavides, G. F.↗

INFLUENCE OF SUPPLEMENTARY ARGON GAS SHIELDING ON THE MICROSTRUCTURE AND MECHANICAL BEHAVIOR OF SS316L ADDITIVELY MANUFACTURED BY DIRECTED ENERGY DEPOSITION

The dissolution of atmospheric gases into parts additively manufactured by directed energy deposition (DED) has long been of concern, and stock shielding solutions have usually proven inadequate at fully removing atmospheric gases from weld beads. The objective of this work was to design a new supplementary argon gas shroud for a specific DED printer and evaluate its effect on microstructure and macroscopic properties of SS316L and the potential for printing more reactive metals such as Ti-6Al-4V. This was investigated by printing four SS316L sample blocks, two with and two without the shroud, each printed in two different orientations. These samples were subsequently evaluated with inert gas fusion (IGF), SEM/EDS imaging, and tensile tests. The shroud reduced oxygen content by 0.019-0.031%, and SEM imaging revealed fewer oxide inclusions. A more dramatic reduction of 0.13% oxygen and 0.171% nitrogen was observed by the inert gas fusion of Ti-6Al-4V samples. Overall, the results indicated the shroud was successful at reducing atmospheric gas uptake within the print region and may enable the printing of reactive metal powders in DED systems.

Helvie, Kyle↗

F + H2 collisions on two electronic potential energy surfaces - Quantum-mechanical study of the collinear reaction

Collinear quantum calculations are carried out for reactive F + H2 collisions on two electronic potential energy surfaces. The resulting transmission and reflection probabilities exhibit much greater variation with energy than single-surface studies would lead us to anticipate. Transmission to low-lying product channels is increased by orders of magnitude by the presence of the second surface; however, branching ratios among product states are found to be independent of the initial electronic state of the reactants. These apparently contradictory aspects of the calculation are discussed and a tentative explanation put forward to resolve them.

Zimmerman, I. H.↗

REACTER: A Versatile Tool for Large-Scale Reactive Molecular Dynamics

Accurately describing reactive events over long length and time scales remains a grand challenge of computational materials science. REACTER is a general protocol for modeling chemical reactions using classical force fields, and is implemented in the popular molecular dynamics software LAMMPS. REACTER has a growing user base and has been used as a model-building tool for a variety of materials, including thermoplastics, thermosets, glassy materials and composites. The method has also been applied to accelerated modeling of reversible chemical reactions, such as the formation of electrochemical components for batteries. Recently, the REACTER protocol has received some major upgrades to enhance its ability to predict when reactions occur and to make it easier to use. Force field parameters can now be automatically assigned to newly created bonds, angles and other interactions. Advanced reaction constraints have also been added, including an Arrhenius constraint to enforce an effective activation energy, a root-mean-square-deviation option for complex geometrical constraints, and a constraint based on the total potential energy of the atoms involved in a reactive site. This potential energy constraint allows for the accurate reproduction of DFT-based tight-binding (DFTB3) predicted bond dissociation curves for mechanically induced bond breaking.

polymer simulations, molecular dynamics↗

Molecular Processes in Comets

The research focused on molecular hydrogen and its response to ultraviolet radiation, photoelectron impact excitation and X-ray radiation and on the interpretation of the ultraviolet spectra of the Jupiter dayglow and auroras. A systematic effort was made to obtain reliable rate coefficients for rovibrational energy transfer of H2, particularly in collisions with hydrogen atoms. We carried out elaborate quantum-mechanical calculations of the scattering of H and H2 on what had been characterized as a reliable potential energy surface of the H3 molecular system. These calculations took into account reactive channels and rate coefficients for ortho-para transitions were obtained. Quantal calculations are too complex to be applied to all the possible rovibrational transitions and we turned to a semi-classical method. With it we calculated rate coefficients for transitions, reactive and non-reactive, for all the rovibrational levels. We carried out the calculations for three of the available H3 potential energy surfaces. We discovered an unexpected sensitivity of the rate coefficients for the non-reactive channels to the potential energy surface. This discovery stimulated more thorough investigations of the potential energy surface elsewhere and to the construction of a new surface. We have used it in further semi-classical calculations in work that will shortly be 2 completed and which, together with new quantum-mechanical calculations should comprise a set of reliable rate coefficients that can be used in discussions of H2 on the Jovian planets. We carried out a detailed study of the Jovian ultraviolet dayglow. There has been a long-running argument about the dayglow on Jupiter. There are two sources of excitation: fluorescence and photoelectron impact excitation. It had been argued that a third source "the electron glow" was needed to bring theory and observation into agreement. We believe we have shown conclusively that the third source is unnecessary. We have achieved a close quantitative agreement between the predicted spectrum arising from fluorescence and photoelectrons and the measured spectrum. We also demonstrated a method by which the presence of HD could be established observationary. Similar calculations were carried out of the ultraviolet spectra of the Jovian auroras. We again found close agreement. Indeed, the agreement was so detailed we were able to derive the temperature of the atmosphere. We found, contrary to the standard model of the time, a high temperature between 400 K and 600 K and established the presence of a significant temperature gradient. A large temperature gradient was indeed found by direct sampling with the Jupiter probe.

Dalgarno, A.↗

A time-dependent wave packet approach to atom-diatom reactive collision probabilities - Theory and application to the H + H2(J = 0) system

This paper describes a new approach to the study of atom-diatom reactive collisions in three dimensions employing wave packets and the time-dependent Schroedinger equation. The method uses a projection operator approach to couple the inelastic and reactive portions of the total wave function and optical potentials to circumvent the necessity of using product arrangement coordinates. Reactive transition probabilities are calculated from the state resolved flux of the wave packet as it leaves the interaction region in the direction of the reactive arrangement channel. The present approach is used to obtain such vibrationally resolved probabilities for the three-dimensional H + H2 (J = 0) hydrogen exchange reaction, using a body-fixed system of coordinates.

Neuhauser, Daniel↗

The quantum dynamics of electronically nonadiabatic chemical reactions

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally adiabatic functions in various quantum scattering algorithms.

Truhlar, Donald G.↗

Liquid Sorption-Enhanced Haber–Bosch Process

The use of a liquid sorbent in a traditional Haber-Bosch process enables significant improvements in energy efficiency and potential cost savings for arguably the most important chemical process on the planet. The approach presented in this report employs an incompressible liquid sorbent that absorbs and releases ammonia (NH 3 ) under specific conditions. To achieve this, we investigate reactions of ammonia and pure phosphoric acid (H 3 PO 4 , PA), which rapidly neutralize to form an equilibrated solution of monoammonium phosphate (MAP) and diammonium phosphate (DAP) that functions as a reversible and regenerable sorbent. Through intimate contact of the gas-phase Haber-Bosch reaction mixture with this liquid absorbent, complete equilibrium uptake may be achieved in an appropriately sized separator, and facile separation occurs through the use of independent liquid and gas phases. Following depressurization and release of the ammonia product, only the incompressible fluid needs to be repressurized and returned to the reactor. This study documents proof-of-concept absorption and desorption experiments carried out in 75 mL batch reactors, predominantly charged with precise MAP and DAP mixtures that equilibrate at process-relevant temperatures and pressures. We then assemble the first thermodynamic relationships that underlie this advantaged separation strategy, validated by reactive force field (ReaxFF) interatomic potential simulations, and benchmarked with traditional separation routes via process modeling and technoeconomic analysis. The scale of energy consumption in the century-old Haber-Bosch process is massive, and the elegant liquid sorption approach reported here offers opportunities to enhance its energy efficiency for the next frontier of ammonia synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Challenges in Product Selectivity for Electrocatalytic Reduction of Amine-Captured CO 2 : Implications for Reactive Carbon Capture

CO 2 is a potential feedstock for carbon-based fuels or materials, but is only available in dilute streams. Integrated processes for CO 2 capture and conversion directly valorize the CO 2 captured by sorbent materials, skipping the energetically expensive sorbent regeneration step. Amines are the most heavily studied liquid-phase sorbent materials for CO 2 capture from dilute streams. Amines react with CO 2 in a 2:1 ratio to form the corresponding ammonium carbamate. Ammonium carbamate [NH 4 ][H 2 NCO 2 ] was tested as the substrate using the highly selective and robust CO 2 -to-formate reduction electrocatalyst [( tBu POCOP)Ir(H)(NCCH 3 ) 2 ], where ( tBu POCOP) is the tridentate pincer ligand 2,6-bis(di tert -butyl-phosphonito). When ammonium carbamate was used as the substrate instead of CO 2 , only hydrogen was produced. An equivalent electrolysis with ammonium hexafluorophosphate with CO 2 also resulted in primarily hydrogen. Methyl carbamate and urea were also tested as substrates as proxies for carbamate that do not contain an equivalent of ammonium, and there was also negligible reduction to carbon-based products. These results indicate that the loss of selectivity observed for aminecaptured CO 2 , or ammonium carbamate, is likely due to the generation of the acidic ammonium equivalent as well as the greater challenge of reducing carbamate compared to CO 2 . This study illustrates that catalysts with high selectivity for concentrated CO 2 can favor hydrogen evolution and loss of carbon-based products when amine-captured CO 2 is used instead.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface chlorination of IrO2(110) by HCl

The ability to controllably chlorinate metal-oxide surfaces can provide opportunities for designing selective oxidation catalysts. In the present study, we investigated the surface chlorination of IrO2(110) by HCl using temperature programmed reaction spectroscopy (TPRS), x-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. We find that exposing IrO2(110) to HCl, followed by heating to 650 K in ultrahigh vacuum, produces nearly equal quantities of on-top and bridging Cl atoms on the surface, Clt and Clbr, where the Clbr atoms replace O-atoms that are removed from the surface by H2O formation. After HCl adsorption at 85 K, only H2O desorbs at low Cl coverages during TPRS, but HCl begins to desorb in increasing yields as the Cl coverage is increased above about 0.5 monolayer (ML). The desorption of Cl2 was not observed under any conditions, in good agreement with the high barrier for this reaction predicted by DFT. A maximum Cl coverage of 1 ML, with nearly equal coverages of Clt and Clbr atoms, could be generated by reacting HCl with IrO2(110) in UHV. Our results suggest that a kinetic competition between recombinative HCl and H2O desorption under the conditions studied limits the saturation Cl coverage to a value less than the 2 ML maximum predicted by thermodynamics. XPS further shows that the partitioning of Cl between the Clt and Clbr states can be altered by subjecting partially chlorinated IrO2(110) to reductive or oxidative treatments, demonstrating that the Cl site population can change dynamically in response to the gas environment. Our results provide insights for understanding the chlorination of IrO2(110) by HCl and can enable future experimental studies to determine how Cl-modification alters the surface chemical reactivity of IrO2(110) and potentially enhances selectivity toward partial oxidation chemistry.

Chemistry↗

Interfacial dynamics and catalytic behavior of single Ni atom site

Single-atom catalysts (SACs) have garnered significant interest due to their ability to reduce metal particles to the atomic scale, enabling finely tunable local environments and enhanced catalytic properties in terms of reactivity and selectivity. Despite this potential, their application has largely been confined to small-molecule transformations as metal-catalyzed reaction. Here, in this study, we present a diverse single-atom nickel (Ni) catalyst established via a nanoporous carbon (NPC) supported practice. This catalyst represents a breakthrough by achieving the bond formation between carbon and nitrogen and interfacial dynamics in the SAC. The present first principle-based density functional simulations establish the reaction dynamics and catalytic behaviour of such SAC. This dynamic nature comprises an exclusive nitrogen intercalated site showing excellent base effects. This base quickly tunes the interfacial atmosphere, enabling dynamic movement of adatoms into the NPC species, significantly changing the reaction path in Ni SACs due to superior steric effects. The research demonstrates that SACs can extend the capabilities of catalytic systems to include a wider range of complex reactions, offering substantial promise for the development of new, efficient synthetic methods for creating value-added molecular products.

36 MATERIALS SCIENCE↗

Nested Pebble Bed Blanket (NesPeB)

Recent advances in magnetic confinement fusion technology have attracted billions of dollars of investments in startups from venture capitals and corporations, resulting in the development of devices aiming to demonstrate net energy gain in a self-heated burning plasma, such as SPARC (under construction) and others. However, future fusion power plants must operate in regimes that will require technologies far beyond current experience. According to a National Academies of Science, Engineering, and Medicine report, to have nuclear fusion power plants contributing in a timely manner to the planned reduction of atmospheric carbon dioxide, a pilot plant should be built by 2035, and it should demonstrate fusion power production and the performance of the tritium fuel system (requiring a high enough tritium breeding) by 2040. A recognized key technology gap by [26] is the fusion first wall and blanket since no current blanket concept is considered satisfactory or has been built and proven. The first wall and blanket in magnetic fusion reactors form a vital and complex system, as it must satisfy different functions such as power extraction, tritium breeding, plasma containment, radiation shielding, and safety. The list of design requirements is even longer: high enough tritium production for fusion self-sufficiency, low material activation, decay heat and shutdown dose rates, high thermal efficiency, high-capacity factor, high magnets-divertor-vacuum vessel-first wall life, low corrosion, low cost, and intrinsically safe (requiring minimal licensing). Despite fifty-plus years of research, the first wall and blanket concepts proposed suffer from fundamental technical problems and immaturity (TRL=2-3) that jeopardize the timely delivery of a commercial fusion power plant. A fusion first-wall blanket has never been built nor tested, and a "winning", practical functioning design requires enough engineering margins (high enough tritium breeding considering the uncertainty, etc.), manufacturing simplicity, ease of continuous operation, maintenance, and low cost. A new, groundbreaking blanket concept called "Nested Pebble Bed Blanket" (NesPeB) was developed at ORNL under the successful ARPA-E GAMOW FERMI project (patent application allowed by the USPTO). The NesPeB blanket concept addresses current blanket concepts' shortcomings and technical immaturity, paving the way for accelerated delivery of fusion power plants. NesPeB is based on nested pebbles, which are binary-sized lithium-ceramic pebbles enclosed in "Beryllide" perforated and coated spherical shells, which are also binary-sized, stacked on top of each other, forming a "bed" and cooled by Nitrogen gas also "sweeping" the Helium and Tritium generated by the neutron irradiation of Lithium; the vacuum vessel plasma facing material is Molybdenum-96 and -97 with the first wall cooled by Helium while the divertor armor is made of Tungsten. The simulations of the NesPeB blanket using Fusion Reactors Models Integrator (FERMI) are encouraging as they estimate a tritium breeding ratio (TBR) greater than 1.2 using natural Lithium, acceptable pressure drop, and excellent heat transfer properties. Furthermore, the NesPeB blanket is not limited by magneto-hydro-dynamics (MHD) effects, is designed for online refueling, relies on existing tritium extraction technologies, has a simple construction, and limits the corrosion and chemical reactivity problems. NesPeB has the potential to be transformational and disruptive since it can solve all the main, challenging technical problems of fusion device blankets and accelerate a pilot plant delivery for 10 or more years.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Phase II Field Demonstration at Lansing Smith Generating Plant, Southport, Florida (Final Report)

The Final Technical Report: Field Test Design and Pressure Management Strategies for Phase II Field Demonstration of Optimal Pressure Control, Plume Management, and Produced Water Strategies presents the culmination of multi-year efforts under the U.S. Department of Energy’s Brine Extraction and Storage Test (BEST) program, led by EPRI in partnership with Gulf Power at the Plant Smith site near Panama City, Florida. The project was designed to evaluate and demonstrate the technical feasibility of managing subsurface pressures and fluid movement associated with large-scale CO₂ injection, using low-salinity water as a proxy fluid. Through a combination of field injection testing, reservoir modeling, and optimization studies, the research team developed and refined active and passive brine extraction strategies aimed at controlling injection-induced pressure buildup, mitigating risks of fault activation, and managing plume migration. The field demonstration incorporated a new injection well (TIW-2), a new monitoring/extraction well (TEMW-A), and an existing well (TIW-1) repurposed for passive pressure relief. Complementary geophysical monitoring was designed to track plume development and evaluate the effectiveness of pressure management strategies. The report details the integrated workflow encompassing wellfield development, regulatory permitting, model calibration, and survey design. It includes a comprehensive electromagnetic (EM) modeling and inversion study used to develop a cost-effective, time-lapse geophysical monitoring plan capable of imaging the evolving low-salinity plume within the highly saline Lower Tuscaloosa formation. Reservoir simulation results guided the design of the 17-month injection program and the timing of active extraction to maintain formation pressures below a hypothetical fault reactivation threshold. Supporting analyses evaluated potential injectivity risks related to clay fines migration and geochemical incompatibility, identifying practical mitigation measures such as salinity and pH control. The final design recommends a series of crosswell EM surveys—conducted before, during, and after injection—as the most effective and economical approach for plume imaging, supplemented by continuous downhole pressure and flow monitoring. Collectively, the study provides a field-ready framework for cost-effective pressure management and monitoring in support of future CO₂ storage projects.

01 COAL, LIGNITE, AND PEAT↗

HESTIA Phase I Test Results: The Air Revitalization System

In any human spaceflight mission, a number of Environmental Control & Life Support System (ECLSS) technologies work together to provide the conditions astronauts need to live healthily, productively, and comfortably in space. In a long-duration mission, many of these ECLSS technologies may use materials supplied by In-Situ Resource Utilization (ISRU), introducing more interactions between systems. The Human Exploration Spacecraft Test-bed for Integration & Advancement (HESTIA) Project aims to create a test-bed to evaluate ECLSS and ISRU technologies and how they interact in a high-fidelity, closed-loop, human-rated analog habitat. Air purity and conditioning are essential components within any ECLSS and for HESTIA's first test they were achieved with the Air Revitalization System (ARS) described below. The ARS provided four essential functions to the test-bed chamber: cooling the air, removing humidity from the air, removing trace contaminants, and scrubbing carbon dioxide (CO2) from the air. In this case, the oxygen supply function was provided by ISRU. In the current configuration, the ARS is a collection of different subsystems. A fan circulates the air, while a condensing heat exchanger (CHX) pulls humidity out of the air. A Trace Contaminant Removal System (TCRS) filters the air of potentially harmful contaminants. Lastly, a Reactive Plastic Lithium Hydroxide (RP-LiOH) unit removes CO2 from the breathing air. During the HESTIA Phase I test in September 2015, the ARS and its individual components each functioned as expected, although further analysis is underway. During the Phase I testing and in prior bench-top tests, the energy balance of heat removed by the CHX was not equal to the cooling it received. This indicated possible instrument error and therefore recalibration of the instruments and follow-up testing is planned in 2016 to address the issue. The ARS was tested in conjunction with two other systems: the Human Metabolic Simulator (HMS) and the Electrolyzer. They behaved as anticipated as well. The HMS added humidity, CO2, and heat to the chamber while removing oxygen, and the Electrolyzer (an ISRU technology) added oxygen. The objective for HESTIA in 2015 was achieved: the creation of a high-fidelity test-bed for ECLSS and ISRU technologies. With the 'backbone' technologies installed, more technologies will be added to increase the analog habitat's fidelity over the next few years. The ARS was designed with this in mind, and as new technologies develop and mature, the strategic installation of the existing components will allow for them to be replaced with the new technologies.

Wright, Sarah E.↗

Global and Regional Temperature-change Potentials for Near-term Climate Forcers

The emissions of reactive gases and aerosols can affect climate through the burdens of ozone, methane and aerosols, having both cooling and warming effects. These species are generally referred to near-term climate forcers (NTCFs) or short-lived climate pollutants (SLCPs), because of their short atmospheric residence time. The mitigation of these would be attractive for both air quality and climate on a 30-year timescale, provided it is not at the expense of CO2 mitigation. In this study we examine the climate effects of the emissions of NTCFs from 4 continental regions (East Asia, Europe, North America and South Asia) using results from the Task Force on Hemispheric Transport of Air Pollution Source-Receptor global chemical transport model simulations. We address 3 aerosol species (sulphate, particulate organic matter and black carbon - BC) and 4 ozone precursors (methane, reactive nitrogen oxides - NOx, volatile organic compounds VOC, and carbon monoxide - CO). For the aerosols the global warming potentials (GWPs) and global temperature change potentials (GTPs) are simply time-dependent scaling of the equilibrium radiative forcing, with the GTPs decreasing more rapidly with time than the GWPs. While the aerosol climate metrics have only a modest dependence on emission region, emissions of NOx and VOCs from South Asia have GWPs and GTPs of higher magnitude than from the other northern hemisphere regions. On regional basis, the northern mid-latitude temperature response to northern mid-latitude emissions is approximately twice as large as the global average response for aerosol emission, and about 20-30% larger than the global average for methane, VOC and CO emissions. We also found that temperatures in the Arctic latitudes appear to be particularly sensitive to black carbon emissions from South Asia.

climate forcer↗

Plasma Cytokine Levels in Astronauts Before and after Spaceflight

Space flight is a unique experience and results in adverse effects on human physiology. Changes have been reported in various physiological systems, including musculoskeletal, neurovestibular, cardiovascular, endocrine, immunity and increased latent viral reactivation as well as others. The potential mechanisms behind these changes are not fully understood. Various cytokines such as IL-1, IL-6, TNF and chemokines have been linked to several of these changes, like muscle loss, bone loss, fatigue, sleep deprivation and viral reactivation. Eighteen astronauts (15 M and 3 F) from 8 spaceflights and 10 healthy age-matched adults (6 M, 4 F) were included in the present study. A panel of 21 plasma cytokines was analyzed with the Luminex 100 to measure the cytokines in these subjects 10 days before the flight (L-10), 2-3 hour after landing (R+0), 3 days after landing (R+3), and at their annual medical exam (AME). IL-10, IL-1, IFN-alpha, MCP-1 and IP-10 increased significantly at L-10 as compared with AME levels. IL-6 and IFN-alpha showed significant increases at R + 0 (P less than .05) over their baseline levels (AME). Cytokine levels at R+3 were not significantly different from R+0. IL-10 and IL-6 have been reported to increase in during viral reactivation. These data show that there was a shift from TH1 to TH2 cytokines L-10 and R+0. We also studied viral reactivation in 10 of the 18 subjects included in the present study before, during, and after space flight. Increased salivary varicella zoster virus (VZV) shedding in these subjects was found either during or after the mission. VZV shedding correlated with the increased levels of cytokines especially IL-10 and IL-6. Overall, our data suggests that cytokines may play an important role in regulating adverse changes in astronauts, and further studies are needed to fully understand the mechanism.

Mehta, Satish K.↗

Mitigating Problems in Measuring Hypergolic Fuels

To monitor hydrazine concentrations accurately and safely, hydrazine is converted into a stable derivative that will be monitored and correlated to the actual hydrazine concentration. The hydrazine's reactivity is harnessed to produce a chemical reaction that will form a stable gas-phase derivative which will not react or decompose before it reaches the detector. Hydrazine, monomethylhydrazine, and unsymmetrical dimethylhydrazine belong to a class of compounds known as hypergolic fuels. These fuels self-ignite upon mixing with hypergolic oxidizer (dinitrogen tetroxide), without need of a spark or other ignition source. The resulting reaction produces thrust with exceptionally high energy, making these compounds particularly useful as rocket propellants. Hydrazines are also highly toxic and corrosive. The combined properties of reactivity, corrosivity, and toxicity present the potential for a leak, a disastrous situation in a hypergol-loaded system. Consequently, leak detection is of the utmost importance in protecting equipment and personnel. Hydrazine vapor quantification presents many challenges in addition to the safety concerns. The reactivity of these compounds causes thermal and catalytic decomposition, which results in significant losses. Further complications arise from the sticky nature of hydrazine. Molecules adsorb irreversibly to virtually any surface they make contact with before detection, which results in instrument drift. These properties make it difficult to accurately quantify hydrazines. Current analytical methods seek to minimize these interactions. After an extensive literature search to determine appropriate chemical reactions, a method was devised to quantify hydrazines, without the limitations of monitoring hydrazines.

Source record↗