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At least 649 records · Page 36

Acid rain at Kennedy Space Center, Florida - Recent observations

During the period July, 1977 to September, 1979, rainfall was collected in the vicinity of the Kennedy Space Center and subjected to appropriate chemical analysis for purposes of characterization of general composition and acidity. Results obtained form the basis for future comparisons, should significant alteration of the chemical composition of rain occur during the space shuttle era. Acidity extremes calculated on a monthly basis from event samples collected from five sites within a 200 sq km area varied from pH 5.1 in November, 1977, and April, 1978 to pH 4.3 in July, 1978 and July, 1979. Weighted average pH for the entire period was 4.55. Acidity was due to the presence of sulfuric and nitric acids. The mole ratio of excess SO4(-2):NO3(-) was typically greater than one. Monthly weighted average Cl(-) concentrations ranged from 20-240 micromoles/liter. The Cl(-):Na(+) ratio was slightly lower than that present in sea water.

Madsen, B. C.↗

Isotopic composition and concentration of sulfur in carbonaceous chondrites

New sulfur isotopic ratio measurements are reported for seven carbonaceous chondrites. Newly developed procedures permit measurement of delta S-33, delta S-34, and delta S-36 at precisions significantly greater than previously reported. A search for S-36 nucleosynthetic anomalies coproduced with anomalies in, for example, Ti-50 and Ca-48 was negative. The high endemic sulfur concentration probably dilutes any S-36 anomaly, and separation of individual sulfur phases may be needed to identify S-36 carrier phases. Large internal isotopic variations are observed, deriving from parent body and possibly nebular processes. Chondrule separates from Allende demonstrate isotopic compositions which vary as a function of diameter. High-temperature gas-solid exchange and a two-component mixing model may account for the observations. High-resolution isotopic data and structural information are reported for organic sulfur compounds separated by chemical extractions. The insoluble organics appear to be of either aliphatic or alicyclic structure and are dominant phases.

Gao, Xia↗

The differences between mass- and light-derived structural parameters over time for MaNGA elliptical galaxies

ABSTRACT We apply stellar population synthesis analysis to obtain spatially resolved archaeological inferences for a large sample of ‘red and dead’ Elliptical galaxies (Classical Ellipticals, CLEs) from the MaNGA/SDSS-IV DR15 survey. From their 2D stellar light and mass maps, we explore the differences between the radial mass and light distributions in the rest-frame bands g, r, and i as functions of look-back time, tlb, or redshift, z. We characterize these differences through the ratios between the following mass- and light-derived global properties: sizes, concentrations, and effective surface densities. We find that the mass-to-light ratios of these properties change with tlb, more the more massive the galaxies are. The CLE galaxy archaeological progenitors are, on average, less compact, concentrated, and dense in light than in mass as z decreases. However, at later times, when also the evolution of the progenitors becomes passive at all radii, there is an upturn in these trends and the differences between mass and light in compactness/concentration decrease towards z ∼ 0. The trends in the ratios of mass-to-light sizes agree qualitatively with results from direct observations in galaxy surveys at different redshifts. We discuss the caveats and interpretations of our results, and speculate that the strong structural evolution found in some previous studies for early-type galaxies could be explained partially by photometric changes rather than by intrinsic structural changes.

Ibarra-Medel, H. (ORCID:0000000297906313)↗

Hydrodynamics of Relativistic Fireballs

Many models of gamma-ray bursts involve a fireball, which is an optically thick concentration of radiation energy with a high ratio of energy density to rest mass. We examine analytically and numerically the evolution of a relativistic fireball. We show that, after an early rearrangement phase, most of the matter and energy in the fireball is concentrated within a narrow shell. The shell propagates at nearly the speed of light, with a frozen radial profile, and according to a simple set of scaling laws. The spectrum of the escaping radiation is harder at early times and softer later on. Depending on the initial energy-to-mass ratio, the final outcome of a fireball is either photons with roughly the initial temperature or ultrarelativistic baryons. In the latter case, the energy could be converted back to gamma-rays via interaction with surrounding material.

Piran, Tsvi↗

Galaxy–halo size relation from Sloan Digital Sky Survey Data Release 7 and the ELUCID simulation

ABSTRACT Based on galaxies in the Sloan Digital Sky Survey Data Release 7 and dark matter haloes in the dark matter only, cosmological, and constrained ELUCID simulation, we investigate the relation between the observed radii of central galaxies with stellar mass $\gtrsim\!{10}^{8} \, h^{-2}\, {\rm M}_\odot$ and the virial radii of their host dark matter haloes with virial mass $\gtrsim\!{10}^{10.5} \, h^{-1}\, {\rm M}_\odot$, and the dependence of galaxy–halo size relation on the halo spin and concentration. Galaxies in observation are matched to dark matter (sub)haloes in the ELUCID simulation using a novel neighbourhood subhalo abundance matching method. For galaxy two-dimensional (2D) half-light radii R50, we find that early- and late-type galaxies have the same power-law index 0.55 with $R_{50} \propto R_{\rm vir}^{0.55}$, although early-type galaxies have smaller 2D half-light radii than late-type galaxies at fixed halo virial radii. When converting the 2D half-light radii R50 to 3D half-mass radii r1/2, both early- and late-type galaxies display similar galaxy–halo size relations with $\log r_{1/2} = 0.55 \log (R_{\rm vir}/210 \, h^{-1}\, {\rm kpc}) + 0.39$. We find that the galaxy–halo size ratio r1/2/Rvir decreases with increasing halo mass. At fixed halo mass, there is no significant dependence of galaxy–halo size ratio on the halo spin or concentration.

Astronomy & Astrophysics↗

On Lateral Viscosity Contrast in the Mantle and the Rheology of Low-Frequency Geodynamics

Mantle-wide heterogeneity is largely controlled by deeply penetrating thermal convective currents. These thermal currents are likely to produce significant lateral variation in rheology, and this can profoundly influence overall material behaviour. How thermally related lateral viscosity variations impact models of glacio-isostatic and tidal deformation is largely unknown. An important step towards model improvement is to quantify, or bound, the actual viscosity variations that characterize the mantle. Simple scaling of viscosity to shear-wave velocity fluctuations yields map-views of long- wavelength viscosity variation. These give a general quantitative description and aid in estimating the depth dependence of rheological heterogeneity throughout the mantle. The upper mantle is probably characterized by two to four orders of magnitude variation (peak-to-peak). Discrepant time-scales for rebounding Holocene shorelines of Hudson Bay and southern Iceland are consistent with this characterization. Results are given in terms of a local average viscosity ratio, (Delta)eta(bar)(sub i), of volumetric concentration, phi(sub i). For the upper mantle deeper than 340 km the following reasonable limits are estimated for (delta)eta(bar) approx. equal 10(exp -2): 0.01 less than or equal to phi less than or equal to 0.15. A spectrum of ratios (Delta)eta(bar)(sub i) less than 0.1 at concentration level eta(sub i) approx. equal 10(exp -6) - 10(exp -1) in the lower mantle implies a spectrum of shorter time-scale deformational response modes for second-degree spherical harmonic deformations of the Earth. Although highly uncertain, this spectrum of spatial variation allows a purely Maxwellian viscoelastic rheology simultaneously to explain all solid tidal dispersion phenomena and long-term rebound-related mantle viscosity. Composite theory of multiphase viscoelastic media is used to demonstrate this effect.

Ivins, Erik R.↗

Acoustics and Trust of Separate-Flow Exhaust Nozzles With Mixing Devices for High-Bypass-Ratio Engines

The NASA Glenn Research Center recently completed an experimental study to reduce the jet noise from modern turbofan engines. The study concentrated on exhaust nozzle designs for high-bypass-ratio engines. These designs modified the core and fan nozzles individually and simultaneously. Several designs provided an ideal jet noise reduction of over 2.5 EPNdB for the effective perceived noise level (EPNL) metric. Noise data, after correcting for takeoff thrust losses, indicated over a 2.0-EPNdB reduction for nine designs. Individually modifying the fan nozzle did not provide attractive EPNL reductions. Designs in which only the core nozzle was modified provided greater EPNL reductions. Designs in which core and fan nozzles were modified simultaneously provided the greatest EPNL reduction. The best nozzle design had a 2.7-EPNdB reduction (corrected for takeoff thrust loss) with a 0.06-point cruise thrust loss. This design simultaneously employed chevrons on the core and fan nozzles. In comparison with chevrons, tabs appeared to be an inefficient method for reducing jet noise. Data trends indicate that the sum of the thrust losses from individually modifying core and fan nozzles did not generally equal the thrust loss from modifying them simultaneously. Flow blockage from tabs did not scale directly with cruise thrust loss and the interaction between fan flow and the core nozzle seemed to strongly affect noise and cruise performance. Finally, the nozzle configuration candidates for full-scale engine demonstrations are identified.

Naseem H Saiyed↗

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↗

Halocarbon concentration patterns associated with frontal passages

The atmospheric mixing ratios of CCl2F2 (F-12) and CCl3F (F-11) increase abruptly up to 14 ppt (F-12) and 8 ppt (F-11) after strong cold fronts pass and decrease abruptly after warm fronts pass at a semicontinuous monitoring station near Pullman, WA (46 deg 42 min N, 117 deg 10 min W). It is concluded that air masses from higher latitudes (above 60 deg N) can have F-12 and/or F-11 concentrations as much as 5 percent higher than mid-latitude air masses. Conversely, nitrous oxide shows no significant changes during frontal passages and is uniformly distributed between air masses.

Carter, M. W.↗

Modulating Ce 3+ Sites in Ce-Zr Oxide Nanocatalysts through Protamine Biomineralization for Organophosphate Dephosphorylation

Catalytic is a crucial reaction for environmental detoxication of pesticides and neutralization of various molecules classified as chemical warfare agents. Herein, we report on a series of tunable Ce-Zr-based metal oxides, (Zr a Ce 1–a O x ) prepared using a facile biomineralization technique, as catalysts for organophosphates dephosphorylation. Synchrotron scattering and spectroscopy methods showcase that Zr a Ce 1–a O x catalysts are highly defective and exhibit an abundance of Ce 3+ sites that promote oxygen vacancies needed for enhanced dephosphorylation reactions. The catalytic performance was assessed using a model para-nitrophenyl phosphate reaction and showcases a strong dependence on Zr dopant concentration and subsequent tuning of the Ce 3+ /Ce 4+ ratio. Analysis of synchrotron datasets allowed structure-performance correlations between the Ce 3+ concentration and associated oxygen vacancies, the dephosphorylation rate constant, and Zr concentration to be established, confirming that Ce 3+ as active sites is positively correlated with the rate constant. We envision that similar biomineralization approaches can be used to fabricate Ce 3+ -rich Ce-Zr oxide for environmental application in dephosphorylation and other hydrolysis reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rhodium‐Catalyzed Oxidative Alkenylation of Naphthalene: Factors That Influence Reaction at the β‐ versus α‐Position

The catalyst precursor [(η 2 -C 2 H 4 ) 2 Rh(μ-OAc)] 2 and in situ oxidant Cu(OPiv) 2 (OPiv = t-BuCOO – ) convert naphthalene and olefins (i.e., ethylene and propylene) to alkenylnaphthalenes. Under all reaction conditions tested, the functionalization is selective for the β-position of naphthalene with the highest observed β:α ratio >20:1. The β-selectivity is catalyst controlled, but oxidant identity, ethylene pressure, and olefin identity influence the ratio of β-alkenylation to α-alkenylation. The concentration of HOPiv and naphthalene do not have an effect on the β:α ratio under the reaction conditions tested. Arenes similar to naphthalene (i.e., o-xylene and 1,2,3,4-tetrahydronaphthalene) give quantitative selectivity for alkenylation at the position β to the substituent. Using propylene as the olefin for naphthalene alkenylation, the β:α ratio is 32(7):1. and the anti-Markovnikov to Markovnikov ratio is 16(2):1.

Alkenes↗

Adhesion, friction, and wear of binary alloys in contact with single-crystal silicon carbide

Sliding friction experiments, conducted with various iron base alloys (alloying elements are Ti, Cr, Mn, Ni, Rh and W) in contact with a single crystal silicon carbide /0001/ surface in vacuum are discussed. Results indicate atomic size misfit and concentration of alloying elements play a dominant role in controlling adhesion, friction, and wear properties of iron-base binary alloys. The controlling mechanism of the alloy properties is as an intrinsic effect involving the resistance to shear fracture of cohesive bonding in the alloy. The coefficient of friction generally increases with an increase in solute concentration. The coefficient of friction increases as the solute-to-iron atomic radius ratio increases or decreases from unity. Alloys having higher solute concentration produce more transfer to silicon carbide than do alloys having low solute concentrations. The chemical activity of the alloying element is also an important parameter in controlling adhesion and friction of alloys.

Miyoshi, K.↗

The adhesion, friction, and wear of binary alloys in contact with single-crystal silicon carbide

Sliding friction experiments were conducted with various iron-base alloys (alloying elements were Ti, Cr, Ni, Rh, and W) in contact with a single-crystal silicon carbide (0001) surface in vacuum. Results indicate atomic size misfit and concentration of alloying elements play a dominant role in controlling adhesion, friction, and wear properties of iron-base binary alloys. The controlling mechanism of the alloy properties is an intrinsic effect involving the resistance to shear fracture of cohesive bonding in the alloy. The coefficient of friction generally increases with an increase in solute concentration. The coefficient of friction increases as the solute-to-iron atomic radius ratio increases or decreases from unity. Alloys having higher solute concentration produce more transfer to silicon carbide than do alloys having low solute concentrations. The chemical activity of the alloying element is also an important parameter in controlling adhesion and friction of alloys.

Miyoshi, K.↗

BOREAS TE-5 CO2 Concentration and Stable Isotope Composition

The BOREAS TE-5 team collected measurements in the NSA and SSA on gas exchange, gas composition, and tree growth. This data set contains measurements of the concentration and stable carbon (C-13/C-12 and oxygen (O-18/O-16) isotope ratios of atmospheric CO2 in air samples collected at different heights within forest canopies. The data were collected to determine the influence of photosynthesis and respiration by the forest ecosystems on the concentration and stable isotope ratio of atmospheric CO2 These measurements were collected at the SSA during each 1994 IFC at OJP, OBS, and OA sites. Measurements were also collected at the NSA during each 1994 IFC at the OJP, T6R5S TE UBS, and T2Q6A TE OA sites. The stable isotope ratios are expressed using standard delta notation and in units of per mil. The isotope ratios are expressed relative to the international standard, PDB, for both carbon and oxygen samples. The data are stored in tabular ASCII files. The data files are available on a CD-ROM (see document number 20010000884), or from the Oak Ridge National Laboratory (ORNL) Distributed Activity Archive Center (DAAC).

Hall, Forrest G.↗

Rhenium Isotope Reconnaissance of Uranium Ore Concentrates

Exploration of natural isotopic variations of the element rhenium (Re) is in its infancy, with initial studies revealing isotopic fractionation in a variety of geological materials. Here, in this work, we investigate Re isotope variation as a new geochemical tool, given its redox-sensitive properties and affinity for organic matter and sulfides. In this work, Re abundance and isotope ratio data were collected from uranium ore concentrates (UOCs) across a variety of depositional ages, locations, geologic settings, and deposit types. Ore types from which the UOC were derived include sandstone, unconformity, and quartz-pebble (QP) conglomerate. To isolate Re from the U-rich matrix of UOCs, a new purification method utilizing DGA ion exchange resin was developed. We found that UOCs exhibit a wide range of Re isotope ratios, with sandstone ore-derived UOCs having the isotopically lightest values, QP conglomerate ore-derived UOCs having the heaviest, and unconformity ore-derived UOCs in between (with some overlap with sandstone UOCs). The Re isotope ratio range observed in UOCs extends previously reported values by more than a factor of two. Industrial processing (e.g., incomplete recovery of Re from ore, contamination, fractionation during processing) may play a role in the isotopic variability in the UOCs. However, systematic differences between ore types suggest that the depositional setting is a significant factor. For nuclear forensic investigations, Re isotopic compositions combined with data from other isotopic systems provide geochemical signatures that can aid in provenance assessment of UOCs. Regardless of the specific causes for the wide range of Re isotope ratios in UOCs, these initial data indicate Re is a promising tool for nuclear forensic investigations on samples from early in the nuclear fuel cycle.

58 GEOSCIENCES↗

Quantitative mapping by remote sensing of an ocean acid-waste dump

Results from quantitative analysis show that airplane remotely sensed spectral data can be used to quantify and map an acid-waste dump in terms of its particulate iron concentration. These same data, however, could not be used to map the dump in terms of total suspended solids, organic suspended solids, or inorganic suspended solids concentrations. A single-variable equation using the ratio of band 2 (440 to 490 nm) radiance to band 4 (540 to 580 nm) radiance was used to quantify the iron concentration in the acid-waste dump. The acid waste that was mapped varied in age from freshly dumped to 31/2 hr. Particulate iron concentrations in the acid waste were estimated to range up to 1.1 mg/l at a depth of 0.46 m. A classification technique was developed to identify pixels in the data set affected by sun glitter.

Ohlhorst, C. W.↗

Revisiting the Effectiveness Of HCHO/NO2 Ratios for Inferring Ozone Sensitivity to Its Precursors Using High Resolution Airborne Remote Sensing Observations in A High Ozone Episode During the KORUS-AQ Campaign

The nonlinear chemical processes involved in ozone production (P(O3)) have necessitated using proxy indicators to convey information about the primary dependence of P(O3) on volatile organic compounds (VOCs) or nitrogen oxides (NOx). In particular, the ratio of remotely sensed columns of formaldehyde (HCHO) to nitrogen dioxide (NO2) has been widely used for studying O3 sensitivity. Previous studies found that the errors in retrievals and the incoherent relationship between the column and the near-surface concentrations are a barrier in applying the ratio in a robust way. In addition to these obstacles, we provide calculational-observational evidence, using an ensemble of 0-D photochemical box models constrained by DC-8 aircraft measurements on an ozone event during the Korea-United States Air Quality (KORUS-AQ) campaign over Seoul, to demonstrate the chemical feedback of NO2 on the formation of HCHO is a controlling factor for the transition line between NOx-sensitive and NOx-saturated regimes. A fixed value (~2.7) of the ratio of the chemical loss of NOx (LNOx) to the chemical loss of HO2+RO2 (LROx) perceptibly differentiates the regimes. Following this value, data points with a ratio of HCHO/NO2 less than 1 can be safely classified as NOx-saturated regime, whereas points with ratios between 1 and 4 fall into one or the other regime. We attribute this mainly to the HCHO-NO2 chemical relationship causing the transition line to occur at larger (smaller) HCHO/NO2 ratios in VOC-rich (VOC-poor) environments. We then redefine the transition line to LNOx/LROx~2.7 that accounts for the HCHO-NO2 chemical relationship leading to HCHO = 3.7 × (NO2 – 1.14 × 1016 molec.cm-2). Although the revised formula is locally calibrated (i.e., requires for readjustment for other regions), its mathematical format removes the need for having a wide range of thresholds used in HCHO/NO2 ratios that is a result of the chemical feedback. Therefore, to be able to properly take the chemical feedback into consideration, the use of HCHO = a × (NO2 – b) formula should be preferred to the ratio in future works. We then use the Geostationary Trace gas and Aerosol Sensor Optimization (GeoTASO) airborne instrument to study O3 sensitivity in Seoul. The unprecedented spatial (250 × 250 m2) and temporal (~every 2 h) resolutions of HCHO and NO2 observations form the sensor enhance our understanding of P(O3) in Seoul; rather than providing a crude label for the entire city, more in-depth variabilities in chemical regimes are observed that should be able to inform mitigation strategies correspondingly.

KORUS-AQ; formaldehyde; NOx; VOC; OMI; GeoTASO; oz↗

Thermal Structure of the TTL and Its Relation to Stratospheric-Tropospheric Exchange of Water

This document describes the annual cycle of the trajectory track line (TTL) fine scale thermal structure as captured by global positioning system (GPS) radio occultation and the pressure levels of the East Meets West Foundation (EMWF) weather analysis. This annual cycle is compared to the annual cycle in water concentrations measured by the HALogen Occultation Experiment (HALOE). A comparison between saturation mixing ratios at the temperatures captured by GPS radio occultation and HALOE concentrations of water vapor shows an annual cycle that is dominated by supersaturation in the boreal winter months, when the upward mass fluxes are larger, and subsaturation in the summer. The longitudinal dependence of these cycles is discussed as well as the possible implications for the seasonality of stratospheric-troposheric exchanges of water.

climates↗