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At least 505 records · Page 28

Application of OMI Observations to a Space-Based Indicator of NOx and VOC Controls on Surface Ozone Formation

We investigated variations in the relative sensitivity of surface ozone formation in summer to precursor species concentrations of volatile organic compounds (VOCs) and nitrogen oxides (NOx) as inferred from the ratio of the tropospheric columns of formaldehyde to nitrogen dioxide (the "Ratio") from the Aura Ozone Monitoring Instrument (OMI). Our modeling study suggests that ozone formation decreases with reductions in VOCs at Ratios less than 1 and NOx at Ratios greater than 2; both NOx and VOC reductions may decrease ozone formation for Ratios between 1 and 2. Using this criteria. the OMI data indicate that ozone formation became: 1. more sensitive to NOx over most of the United States from 2005 to 2007 because of the substantial decrease in NOx emissions, primarily from stationary sources, and the concomitant decrease in the tropospheric column of NO2. and 2. more sensitive to NOx with increasing temperature, in part because emissions of highly reactive, biogenic isoprene increase with temperature, thus increasing the total VOC reactivity. In cities with relatively low isoprene emissions (e.g .. Chicago). the data clearly indicate that ozone formation became more sensitive to NOx from 2005 to 2007. In cities with relatively high isoprene emissions (e.g ., Atlanta), we found that the increase in the Ratio due to decreasing NOx emissions was not obvious as this signal was convolved with variations in the Ratio associated with the temperature dependence of isoprene emissions and, consequently, the formaldehyde concentration.

Duncan, Bryan N.↗

Circadian Effects on Simple Components of Complex Task Performance

The goal of this study was to advance understanding and prediction of the impact of circadian rhythm on aspects of complex task performance during unexpected automation failures, and subsequent fault management. Participants trained on two tasks: a process control simulation, featuring automated support; and a multi-tasking platform. Participants then completed one task in a very early morning (circadian night) session, and the other during a late afternoon (circadian day) session. Small effects of time of day were seen on simple components of task performance, but impacts on more demanding components, such as those that occur following an automation failure, were muted relative to previous studies where circadian rhythm was compounded with sleep deprivation and fatigue. Circadian low participants engaged in compensatory strategies, rather than passively monitoring the automation. The findings and implications are discussed in the context of a model that includes the effects of sleep and fatigue factors.

circadian effects↗

Studies of the mechanisms of turbine fuel instability

The formation of insoluble deposits in a Jet A, a Diesel, and a model fuel (1/10 v/v tetralin/dodecane) was studied. Experiments were conducted using glass containers at 394 K with an air/fuel ratio of 14/1. The effects of addition of ppm levels of various compounds on deposit formation were evaluated. Nitrogen heterocycles were shown to produce a basicity dependent acceleration of deposition. Thiols and thiophene were shown to increase deposition while sulfides and disulfides act as inhibitors. Copper metal and its salts also promote deposition. Results of various instrumental analyses of deposits and development of a high performance liquid chromatographic method for monitoring deposit precursors are discussed.

Daniel, S. R.↗

Origin of life

The pathways of organic chemical synthesis, the chemical evolution on the early Earth leading to life was constrained by the development of the planet by accretion and core formation. The accretion and differentiation into the core-mantle-crust-atmosphere system strongly influenced the temperature and composition of the atmosphere, surface, and interior; but large gaps persist in our understanding of these processes. The time-span over which Earth acquired its volatiles, the composition of these volatiles, and the conditions under which outgassing of volatiles occurred to form the atmosphere, are unknown. Uncertainties in existing models for Earth accretion and early planetary development allows a wide range of possible prebiotic atmospheric compositions at the time and temperature when liquid water appeared and thermally-labile organic compounds could survive. These compositions range from strongly reducing atmospheres to mildly reducing ones.

Chang, S.↗

A novel directly coupled gradostat

The original bidirectional compound chemostat (gradostat) described by Lovitt and Wimpenny has been simplified by making a more compact apparatus in which chemical gradients are established by diffusion between adjacent culture chambers. The experimental model (diffusion coupled (DC) gradostat) consisted of five chambers whose contents could be agitated by turbines rotating in the horizontal plane on a common shaft. Two biological experiments were designed to reveal the value of the DC gradostat. A methylotroph (Methylophilus methylotrophus) grown in a methanol gradient showed expected changes in cell viability as a function of position in the five vessel array. Cells of two species of photosynthetic bacteria (Rhodobacter capsulata and Rhodopseudomonas marina/agilis) with different salt sensitivities could be mixed and subsequently separated by the DC gradostat operating with a NaCl gradient of 0-3% w/v.

NASA Discipline Exobiology↗

High temperature reformation of aluminum and chlorine compounds behind the Mach disk of a solid-fuel rocket exhaust

Chemical reactions expected to occur among the constituents of solid-fuel rocket engine effluents in the hot region behind a Mach disk are analyzed theoretically. With the use of a rocket plume model that assumes the flow to be separated in the base region, and a chemical reaction scheme that includes evaporation of alumina and the associated reactions of 17 gas species, the reformation of the effluent is calculated. It is shown that AlClO and AlOH are produced in exchange for a corresponding reduction in the amounts of HCl and Al2O3. For the case of the space shuttle booster engines, up to 2% of the original mass of the rocket fuel can possibly be converted to these two new species and deposited in the atmosphere between the altitudes of 10 and 40 km. No adverse effects on the atmospheric environment are anticipated with the addition of these two new species.

Park, C.↗

Cyclic Oxidation Testing and Modelling: A NASA Lewis Perspective

The Materials Division of the NASA Lewis Research Center has been heavily involved in the cyclic oxidation of high temperature materials for 30 years. Cyclic furnace and burner rig apparati have been developed, refined, and replicated to provide a large scale facility capable of evaluating many materials by a standard technique. Material behavior is characterized by weight change data obtained throughout the test, which has been modelled in a step-wise process of scale growth and spallation. This model and a coupled diffusion model have successfully described cyclic behavior for a number of systems and have provided insights regarding life prediction and variations in the spalling process. Performance ranking and mechanistic studies are discussed primarily for superalloys and coating alloys. Similar cyclic oxidation studies have been performed on steels, intermetallic compounds, thermal barrier coatings, ceramics, and ceramic composites. The most common oxidation test was performed in air at temperatures ranging from 800 deg. to 1600 C, for times up to 10000 h, and for cycle durations of 0.1 to 1000 h. Less controlled, but important, test parameters are the cooling temperature and humidity level. Heating and cooling rates are not likely to affect scale spallation. Broad experience has usually allowed for considerable focus and simplification of these test parameters, while still revealing the principal aspects of material behavior and performance. Extensive testing has been performed to statistically model the compositional effects of experimental alloys and to construct a comprehensive database of complex commercial alloys.

Smialek, J. L.↗

RSRA sixth scale wind tunnel test

The sixth scale model of the Sikorsky/NASA/Army rotor systems research aircraft was tested in an 18-foot section of a large subsonic wind tunnel for the purpose of obtaining basic data in the areas of performance, stability, and body surface loads. The model was mounted in the tunnel on the struts arranged in tandem. Basic testing was limited to forward flight with angles of yaw from -20 to +20 degrees and angles of attack from -20 to +25 degrees. Tunnel test speeds were varied up to 172 knots (q = 96 psf). Test data were monitored through a high speed static data acquisition system, linked to a PDP-6 computer. This system provided immediate records of angle of attack, angle of yaw, six component force and moment data, and static and total pressure information. The wind tunnel model was constructed of aluminum structural members with aluminum, fiberglass, and wood skins. Tabulated force and moment data, flow visualization photographs, tabulated surface pressure data are presented for the basic helicopter and compound configurations. Limited discussions of the results of the test are included.

Flemming, R.↗

Phase transitions in Group III-V and II-VI semiconductors at high pressure

The structures and transition pressures of Group III-V and II-VI semiconductors and of a pseudobinary system (Ga/x/In/1-x/Sb) have been investigated. Results indicate that GaP, InSb, GaSb, GaAs and possible AlP assume Metallic structures at high pressures; a tetragonal, beta-Sn-like structure is adopted by only InSb and GaSb. The rocksalt phase is preferred in InP, InAs, AlSb, ZnO and ZnS. The model of Van Vechten (1973) gives transition pressures which are in good agreement with measured values, but must be refined to account for the occurrence of the ionic rocksalt structure in some compounds. In addition, discrepancies between the theoretical scaling values for volume changes at the semiconductor-to-metal transitions are observed.

Yu, S. C.↗

A hybrid model of the CO2 geochemical cycle and its application to large impact events

The effects of a large asteriod or comet impact on modern and ancient marine biospheres are analyzed. A hybrid model of the carbonate-silicate geochemical cycle, which is capable of calculating the concentrations of carbon dioxide in the atmosphere, ocean, and sedimentary rocks, is described. The differences between the Keir and Berger (1983) model and the hybrid model are discussed. Equilibrium solutions are derived for the preindustrial atmosphere/ocean system and for a system similar to that of the late Cretaceous Period. The model data reveal that globl darkening caused by a stratospheric dust veil could destroy the existing phytoplankton within a period of several weeks or months, nd the dissolution of atmospheric NO(x) compounds would lower the pH of ocean surface waters and release CO2 into the atmosphere. It is noted that the surface temperatures could be increased by several degrees and surface oceans would be uninhabitable for calcaerous organisms for approximately 20 years.

Kasting, J. F.↗

New Directions in Phthalocyanine Pigments

The objectives were the following: (1) investigation of the synthesis of new phthalocyanines; (2) characterization of the new phthalocyanines synthesized; (3) investigate the properties of the newly synthesized phthalocyanines with emphasis on UV protection of plastics and coatings; and (4) utilize quantum mechanics to evaluate the structural relationships with possible properties and synthetic approaches. The proposed research targeted the synthesis of phthalocyanines containing an aromatic bridge between two phthalocyanine rings. The goal was to synthesize pigments which would protect plastics when exposed to the photodegradation effects of the sun in space. The stability and extended conjugation of the phthalocyanines offer a unique opportunity for energy absorption and numerous radiative and non-radiative energy loss mechanisms. Although the original targeted phthalocyanines were changed early in the project, several new and unique phthalocyanine compounds were prepared. The basic goals of this work were met and some unique and unexpected outcomes of the work were the result of the integral use of quantum mechanics and molecular modeling with the synthetic effort.

Vandemark, Michael R.↗

Estimates of ozone response to various combinations of NO(x) and VOC emission reductions in the eastern United States

There is increasing recognition that controls on NO(x) emissions may be necessary, in addition to existing and future Volatile Organic Compounds (VOC) controls, for the abatement of ozone (O3) over portions of the United States. This study compares various combinations of anthropogenic NO(x) and VOC emission reductions through a series of model simulations. A total of 6 simulations were performed with the Regional Oxidant Model (ROM) for a 9-day period in July 1988. Each simulation reduced anthropogenic NO(x) and VOC emissions across-the-board by different amounts. Maximum O3 concentrations for the period were compared between the simulations. Comparison of the simulations suggests that: (1) NO(x) controls may be more effective than VOC controls in reducing peak O3 over most of the eastern United States; (2) VOC controls are most effective in urban areas having large sources of emissions; (3) NO(x) controls may increase O3 near large point sources; and (4) the benefit gained from increasing the amount of VOC controls may lessen as the amount of NO(x) control is increased. This paper has been reviewed in accordance with the U.S. Environmental Protection Agency's peer and administrative review policies and approved for presentation and publication. Mention of trade names or commercial products does not constitute endorsement or recommendation for use.

Roselle, Shawn J.↗

Photochemistry Saturn's Atmosphere: Effects of an Influx of External Oxygen - 2

We use a one-dimensional diurnally averaged model of photochemistry and diffusion in Saturn's stratosphere to investigate the influence of extraplanetary debris on atmospheric chemistry. In particular, we consider the effects of an influx of oxygen from micrometeoroid ablation or from ring-particle diffusion; the contribution from cometary impacts, satellite debris, or ring vapor is deemed to be less important. The photochemical model results are compared directly with Infrared Space Observatory (ISO) observations to constrain the influx of extraplanetary oxygen to Saturn. From the ISO observations, we determine that the column densities of CO2 and H2O above 10 mbar in Saturn's atmosphere are (6.3 +/- 1) x 10(exp 14) and (1.4 +/- 0.4) x 10(exp 15)/ square cm, respectively; our models indicate that a globally averaged oxygen influx of (4+/-2) x 10(exp 6) O atoms /sq cm/s is required to explain these observations. Models with a locally enhanced influx of H20 operating over a small fraction of the projected area do not provide as good a fit to the ISO H2O observations. If volatile oxygen compounds comprise one-third to one-half of the exogenic source by mass, then Saturn is currently being bombarded with (3 +/- 2) x 10(exp -16) g/square cm/s of extraplanetary material. To reproduce the observed CO2/H2O ratio in Saturn's stratosphere, some of the exogenic oxygen must arrive in the form of a carbon-oxygen bonded species such as CO or CO2. An influx consistent with the composition of cometary ices fails to reproduce the high observed CO2/H2O ratio, suggesting that (i) the material has ices that are slightly more carbon-rich than is typical for comets, (ii) a contribution from an organic-rich component is required, or (iii) some of the hydrogen-oxygen bonded material is converted to carbon-oxygen bonded material without photochemistry (e.g., during the ablation process). We have also reanalyzed the 5-micron CO observations of Noll and Larson and determine that the CO lines are most sensitive to the 100- to 400-mbar column density for which we derive a range of (0.7-1.5) x 10(exp 17)/square cm; the CO observations do not allow us to distinguish between an external or internal source of CO on Saturn. If we assume that all the extraplanetary oxygen derives from a micrometeoroid source, then the unfocused dust flux at 9.5 AU must be (i) (1 +/- 0.7) x 10(exp -16) g/square cm/s if interstellar grains are the source of the external oxygen on Saturn, (ii) (4 +/- 3) x 10 (exp -17) g/ sq. cm./s if IDPs on randomly inclined, highly eccentric orbits (e.g., Halley-type comet grains) are the source of the external oxygen, or (iii) (2+/- 1.4) x 10(exp -18)/g/sq cm/s if IDPs on low inclination, low eccentricity orbits (e.g., Kuiper-belt grains) are the source of the external oxygen. These estimates can be used in combination with future Cassini dust detection data to determine the ultimate source of the dust at Saturn's distance from the Sun.

Moses, Julianne I.↗

Intermediate Temperature Fluids Life Tests - Theory

There are a number of different applications that could use heat pipes or loop heat pipes (LHPs) in the intermediate temperature range of 450 to 750 K, including space nuclear power system radiators, and high temperature electronics cooling. Potential working fluids include organic fluids, elements, and halides, with halides being the least understood, with only a few life tests conducted. Potential envelope materials for halide working fluids include pure aluminum, aluminum alloys, commercially pure (CP) titanium, titanium alloys, and corrosion resistant superalloys. Life tests were conducted with three halides (AlBr3, SbBr3, and TiCl4) and water in three different envelopes: two aluminum alloys (Al-5052, Al-6061) and Cp-2 titanium. The AlBr3 attacked the grain boundaries in the aluminum envelopes, and formed TiAl compounds in the titanium. The SbBr3 was incompatible with the only envelope material that it was tested with, Al-6061. TiCl4 and water were both compatible with CP2-titanium. A theoretical model was developed that uses electromotive force differences to predict the compatibility of halide working fluids with envelope materials. This theory predicts that iron, nickel, and molybdenum are good envelope materials, while aluminum and titanium halides are good working fluids. The model is in good agreement with results form previous life tests, as well as the current life tests.

Tarau, Calin↗

Ejecta Management in a Safe Lithium Ion Battery Design

As lithium-ion battery energy densities continue to rise, managing the heat and pressure generated during failure events has become increasingly critical. Safety systems must effectively relieve pressure without releasing sparks, flames, or particulate matter, requiring robust filtration solutions. The challenge is compounded by the reduced free volume available for gas expansion in high-density designs, which increases the demands on these filters. While significant progress has been made through experimental studies and modeling efforts to understand the behavior of ejecta during battery failures, there remains a pressing need for practical, rule-of-thumb sizing parameters. These parameters would help correlate high-energy waste streams with appropriate filter design, ensuring reliable containment and safety. This talk will explore recent experimental findings in this area and discuss the potential pathways for developing these essential sizing guidelines.

Ejecta Management↗

A model for the origin of photosynthesis--III. The ultraviolet photochemistry of uroporphyrinogen

The photochemical ramifications of the high ultraviolet flux on the primordial earth prior to the formation of the ozone layer have been considered in a study of the ultraviolet photochemistry of uroporphyrinogen (urohexahydroporphyrin), a colorless compound which absorbs strongly at wavelengths less than 220 nanometers. Urohexahydroporphyrin was investigated since it is the first macrocycle formed on the biosynthetic pathway of chlorophyll and can be used to test the hypothesis that the biosynthetic pathway to chlorophyll recapitulates the evolutionary history of photosynthesis. When urohexahydroporphyrin is illuminated in aqueous anaerobic solution, hydrogen gas is produced. More hydrogen gas is produced in the presence of a colloidal platinum catalyst. The products of the photooxidation of urohexahydroporphyrin are urotetrahydroporphyrin (uroporphomethene) and uroporphyrin. This research shows how the oxidation of uroporphyrinogen to uroporphyrin, the first biogenetic porphyrin, could have occurred anaerobically and abiotically on the primordial earth.

Evolution, Chemical↗

A Relict-Grain-Bearing Porphyritic Olivine Compound Chondrule from LL3.0 Semarkona that Experienced Limited Remelting

Chondrule D8n in LL3.0 Semarkona is a porphyritic olivine (PO) chondrule, 1300 x 1900 microns in size, with a complicated thermal history. The oldest recognizable portion of D8n is a moderately high-FeO, PO chondrule that is modeled as having become enmeshed in a dust ball containing a small, intact, low-FeO porphyritic chondrule and fine-grained material consisting of forsterite, kamacite, troilite, and possibly reduced C. The final chondrule melting event may have been a heat pulse that preferentially melted the low-FeO material and produced a low-FeO, opaque-rich, exterior region, 45-140 microns in thickness, around the original chondrule. Ai one end of the exterior region, a kamacite- and troilite-rich lump 960 pm in length formed. During the final melting event, the coarse, moderately ferroan olivine phenocrysts within the original chondrule appear to have been partly resorbed (These relict phenocrysts have the highest concentrations of FeO, MnO, and Cr2O3-7.5, 0.20, and 0.61 wt%, respectively-in D8n.). Narrow olivine overgrowths crystallized around the phenocrysts following final chondrule melting; their compositions seem to reflect mixing between melt derived from the exterior region and the resorbed margins of the phenocrysts. During the melting event, FeO in the relict phenocrysts was reduced, producing numerous small blebs of Ni-poor metallic Fe along preexisting curvilinear fractures. The reduced olivine flanking the trails of metal blebs has lower FeO than the phenocrysts but virtually identical MnO and Cr2O3 contents. Subsequent parent-body aqueous alteration in the exterior region of the chondrule formed pentlandite and abundant magnetite.

Rubin, Alan E.↗

Diamagnetism and charge transfer in graphite intercalation compounds

The magnetic susceptibilities at 300 K of the acceptor-type intercalation compounds of graphite with Br2 and ICl are calculated; the results are compared with published experimental measurements in graphs; and the charge-transfer parameter f is inferred using a rigid-band model (Loughin et al., 1978; Weinberger et al., 1978; Mattix et al., 1983). Assuming a screening length of 200 pm, the values determined are f = 0.3 for C(8N)Br2 and f = 0.09 for C(13N)ICl.

Tsang, T.↗