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At least 127 records · Page 7

Lagrangian photochemical modeling studies of the 1987 Antarctic spring vortex. I - Comparison with AAOE observations

Results from the Lagrangian photochemical model integrated along computed air parcel trajectories intersected by the ER-2 aircraft are presented and compared with AAOE observations. According to the model, the BrO observations made from the ER-2 within the dehydrated denitrified region are consistent with there being approximately 5 parts per trillion by volume of BrO(y) at 428 K in spring. Within the high ClO region, ozone destruction rates are expected to exceed 2 percent/d with approximately 80 percent due to the ClO dimer mechanism.

Jones, R. L.↗

Software reliability through fault-avoidance and fault-tolerance

Strategies and tools for the testing, risk assessment and risk control of dependable software-based systems were developed. Part of this project consists of studies to enable the transfer of technology to industry, for example the risk management techniques for safety-concious systems. Theoretical investigations of Boolean and Relational Operator (BRO) testing strategy were conducted for condition-based testing. The Basic Graph Generation and Analysis tool (BGG) was extended to fully incorporate several variants of the BRO metric. Single- and multi-phase risk, coverage and time-based models are being developed to provide additional theoretical and empirical basis for estimation of the reliability and availability of large, highly dependable software. A model for software process and risk management was developed. The use of cause-effect graphing for software specification and validation was investigated. Lastly, advanced software fault-tolerance models were studied to provide alternatives and improvements in situations where simple software fault-tolerance strategies break down.

Vouk, Mladen A.↗

Tropospheric Bromine Chemistry: Implications for Present and Pre-industrial Ozone and Mercury

We present a new model for the global tropospheric chemistry of inorganic bromine (Bry) coupled to oxidant-aerosol chemistry in the GEOS-Chem chemical transport model (CTM). Sources of tropospheric Bry include debromination of sea-salt aerosol, photolysis and oxidation of short-lived bromocarbons, and transport from the stratosphere. Comparison to a GOME-2 satellite climatology of tropospheric BrO columns shows that the model can reproduce the observed increase of BrO with latitude, the northern mid-latitudes maximum in winter, and the Arctic maximum in spring. This successful simulation is contingent on the HOBr + HBr reaction taking place in aqueous aerosols and ice clouds. Bromine chemistry in the model decreases tropospheric ozone mixing ratios by <1-8 nmol/mol (6.5% globally), with the largest effects in the northern extratropics in spring. The global mean tropospheric OH concentration decreases by 4 %. Inclusion of bromine chemistry improves the ability of global models (GEOS-Chem and p-TOMCAT) to simulate observed 19th-century ozone and its seasonality. Bromine effects on tropospheric ozone are comparable in the present-day and pre-industrial atmospheres so that estimates of anthropogenic radiative forcing are minimally affected. Br atom concentrations are 40% higher in the pre-industrial atmosphere due to lower ozone, which would decrease by a factor of 2 the atmospheric lifetime of elemental mercury against oxidation by Br. This suggests that historical anthropogenic mercury emissions may have mostly deposited to northern mid-latitudes, enriching the corresponding surface reservoirs. The persistent rise in background surface ozone at northern mid-latitudes during the past decades could possibly contribute to the observations of elevated mercury in subsurface waters of the North Atlantic.

bromine↗

Epitaxial Ferroelectric Hf 0.5 Zr 0.5 O 2 with Metallic Pyrochlore Oxide Electrodes

The synthesis of fully epitaxial ferroelectric Hf 0.5 Zr 0.5 O 2 (HZO) thin films through the use of a conducting pyrochlore oxide electrode that acts as a structural and chemical template is reported. Such pyrochlores, exemplified by Pb 2 Ir 2 O 7 (PIO) and Bi 2 Ru 2 O 7 (BRO), exhibit metallic conductivity with room-temperature resistivity of <1 mΩ cm and are closely lattice matched to yttria-stabilized zirconia substrates as well as the HZO layers grown on top of them. Evidence for epitaxy and domain formation is established with X-ray diffraction and scanning transmission electron microscopy, which show that the c-axis of the HZO film is normal to the substrate surface. The emergence of the non-polar-monoclinic phase from the polar-orthorhombic phase is observed when the HZO film thickness is ≥≈30 nm. Furthermore, thermodynamic analyses reveal the role of epitaxial strain and surface energy in stabilizing the polar phase as well as its coexistence with the non-polar-monoclinic phase as a function of film thickness.

36 MATERIALS SCIENCE↗

Mineral surface-catalyzed oxidation of Mn(II) by bromate: Implications for the occurrence of Mn oxides on Mars

The occurrence of manganese (Mn) oxides on Mars is believed to be an indicator of an O 2 -rich paleoenvironment of Mars because Mn oxides often form through the oxidation of Mn(II) by O 2 on the surface of Earth. An alternative formation pathway was recently proposed, in which Mn(II) is oxidized by bromate (BrO 3 - ), a common oxidant in contemporary Martian regolith. However, the oxidation of Mn(II) by bromate in solution is kinetically controlled and slow unless using very high concentrations (100 mM) of reactants that may be irrelevant to the conditions of Mars. We conducted laboratory simulations to determine whether iron (Fe) oxides (hematite and goethite) and a phyllosilicate (montmorillonite), abundant minerals on the surface of Mars, could catalyze the oxidation of Mn(II) by bromate. Hematite and goethite, but not montmorillonite, dramatically accelerated the oxidation with a low concentration (1 mM) of Mn(II) and bromate under various solution conditions. Further, the reaction system was autocatalytic with Fe oxides initiating the oxidation of Mn(II) at the early stage and the subsequent catalysis mainly provided by the Mn oxide products. In contrast to producing Mn(IV)O 2 only during the homogeneous oxidation of Mn(II) by bromate in solutions, the heterogeneous mineral-surface catalyzed oxidation resulted in a mixture of Mn(III)OOH and Mn(IV)O 2 phases. Mn(III)OOH was an intermediate product and can be further oxidized by bromate to Mn(IV)O 2 . The occurrence and accumulation of the intermediate product MnOOH can be attributed to its rapid formation due to surface-enhanced nucleation and growth on Fe oxide surfaces and to its higher resistance to oxidation by bromate than Mn(III) ions or clusters. Overall, mineralsurface catalyzed oxidation of Mn(II) by bromate is favorable from both thermodynamic and kinetic perspectives, and can be a major pathway for the occurrence of Mn oxides on Mars where microorganisms are lacking to catalyze the reaction. Our study further improves our understanding of the thermodynamic and kinetic controls on Mn(II) oxidation.

54 ENVIRONMENTAL SCIENCES↗

Helper-embedded satellites from an integrase clade that repeatedly targets prophage late genes

Abstract Satellites such as phage-induced chromosomal islands (PICIs) are mobile genetic elements relying on helper phages for their mobilization, through trans-regulatory interactions. We discovered a PICI with a more intimate cis-regulatory configuration, integrated within a late gene of its helper prophage. This helper-embedded PICI (HE-PICI) configuration delays expression of the interrupted helper late gene until the satellite excises and provides passive helper-driven components to both HE-PICI replication and late transcription. Upon induction of a helper-satellite composite, precise excision of the entire composite was observed, followed by composite replication, then satellite excision. We mapped 491 additional HE-PICIs to one of 14 sites in cognates of phage lambda late genes. Associated integrases form a single phylogenetic clade with subclades respecting the 14 site groups, exhibiting repeated tropism for prophage late genes as new integration sites evolve. Four ordered zones in a general gram-negative PICI genome organization are: an integration zone encoding integrase and AlpA, a dynamic zone encoding members of the Bro-N network of domain-swapping DNA-interactive proteins and immunity repressor RNAs, a replication zone, and a dynamic late zone in which clusters as large as 17 consecutive helper prophage late genes have been captured. Helper-embedded satellites present new dimensions in satellite/helper relationships.

Tommasini, Dario↗

Materials Data on NiH12(BrO7)2 by Materials Project

Ni(HO)12(BrO)2 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of two hypobromous acid molecules and one Ni(HO)12 cluster. In the Ni(HO)12 cluster, Ni is bonded in a 6-coordinate geometry to six O atoms. There is four shorter (1.83 Å) and two longer (1.84 Å) Ni–O bond length. There are six inequivalent H sites. In the first H site, H is bonded in a distorted single-bond geometry to two O atoms. There is one shorter (1.01 Å) and one longer (1.67 Å) H–O bond length. In the second H site, H is bonded in a distorted single-bond geometry to two O atoms. There is one shorter (1.01 Å) and one longer (1.66 Å) H–O bond length. In the third H site, H is bonded in a distorted single-bond geometry to two O atoms. There is one shorter (1.01 Å) and one longer (1.67 Å) H–O bond length. In the fourth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.98 Å. In the fifth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.98 Å. In the sixth H site, H is bonded in a single-bond geometry to one O atom. The H–O bond length is 0.98 Å. There are six inequivalent O sites. In the first O site, O is bonded in a water-like geometry to one Ni and one H atom. In the second O site, O is bonded in a water-like geometry to one Ni and one H atom. In the third O site, O is bonded in a water-like geometry to one Ni and one H atom. In the fourth O site, O is bonded in a water-like geometry to two H atoms. In the fifth O site, O is bonded in a water-like geometry to two H atoms. In the sixth O site, O is bonded in a water-like geometry to two H atoms.

36 MATERIALS SCIENCE↗

Materials Data on BrO2 by Materials Project

O2(BrO)2 is alpha carbon monoxide-like structured and crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of two hydrogen peroxide molecules and four hypobromous acid molecules.

36 MATERIALS SCIENCE↗

Materials Data on Te(Br3O4)2 by Materials Project

Te(O2)3(BrO)2(Br)4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of eight hydrobromic acid molecules, four hypobromous acid molecules, two tellurium molecules, and four trioxidane molecules.

36 MATERIALS SCIENCE↗

Absolute rate of the reaction of bromine atoms with ozone from 200-360 K

The rate constant for the reaction Br + O3 yields BrO + O2 was measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at lambda 165nm.O3 was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3, total pressure and limited variations in flash intensity. The measured rate constants obeyed the Arrhenius expression, where the error quoted is two standard deviations. Results are compared with previous determinations which employed the discharge flow-mass spectrometric technique.

Michael, J. V.↗

Absolute rate of the reaction of bromine atoms with ozone from 200 to 360 K

The rate constant for the reaction Br + O3 yields BrO + O2 has been measured from 200 to 360 K by the technique of flash photolysis coupled to time resolved detection of bromine atoms by resonance fluorescence (FP-RF). Br atoms were produced by the flash photolysis of CH3Br at a wavelength of 165 nm. O3 concentration was monitored continuously under reaction conditions by absorption at 253.7 nm. At each of five temperatures the results were independent of substantial variations in O3 concentration, total pressure (Ar), and limited variations in flash intensity (i.e., initial Br concentration). The measured rate constants obey the Arrhenius expression, k = (7.74 plus or minus 0.50) x 10 to the -12th exp(-603 plus or minus 16/T) cu cm/molecule/sec, where the error quoted is two standard deviations.

Michael, J. V.↗

Are Antarctic ozone variations a manifestation of dynamics or chemistry?

The existence of a reverse circulation cell with rising motion in the polar lower stratosphere is suggested as an explanation for the temporal behavior of the ozone column density in the Antarctic region. The upwelling brings ozone-poor air from below 100 mbar to the stratosphere, possibly contributing to the observed ozone decline in early spring. At the same time, the Antarctic stratosphere might contain a very low concentration of NO(x), a condition that could favor a greatly enhanced catalytic removal of O3 by halogen species. It is argued that heterogeneous processes and formation of OClO by the reaction BrO+ClO - OClO+Br before and after the polar night might help to suppress the NO(x) levels during the early spring period.

Tung, K.-K.↗

Chlorine chemistry in the Antarctic stratosphere - Impact of OClO and Cl2O2 and implications for observations

Theories have been proposed to relate the reduction of O3 during Antarctic spring to catalytic cycles involving chlorine and bromine species. A necessary condition for any chlorine-catalyzed scheme is that a large fraction of the chlorine must be in the form of ClO in the lower stratosphere. It has been suggested that these high levels of ClO could be maintained by fast heterogeneous reactions, whose rates are not known at present. Model calculations based on the above mechanisms predict considerable amounts of OClO and Cl2O2, particularly during the night. Results of calculations of the diurnal variations of ClO, OClO, and Cl2O2 during Antarctic spring are presented for different cases. Results from the calculations suggest that coincident measurements of the total column abundance and diurnal variation of ClO and OClO may help constrain key aspects of the proposed chemical mechanisms. Removal of O3 by the catalytic cycle involving Cl2O2 could be as important as that involving BrO for present levels of chlorine, provided that Cl2O2 photolyzes rapidly to yield Cl and ClO2. It is shown that there is no synergy between these two cycles, since they both compete for the available ClO.

Rodriguez, Jose M.↗

Antarctic O3 - Chemical mechanisms for the spring decrease

Chemical explanations for the spring decline of Antarctic O3 involve reactions of ClO or interactions between BrO and ClO. Reaction schemes involving Br radicals have the highest efficiency for removal of O3. The chemical mechanisms require low levels of NO(x). Recent cooling of the stratosphere may have triggered formation of HNO3 monohydrate, removing NO(x) and setting the stage for enhanced loss of ozone over Antarctica.

Mcelroy, Michael B.↗

Chemistry of OClO in the Antarctic stratosphere - Implications for bromine

Previous observations of OClO over the Antarctic obtained in 1986 are used to constrain the stratospheric abundance of bromine. The observed diurnal variation is consistent with the production of OClO via the reaction of ClO with BrO if the branching ratio to the BrCl channel is between 3.5 and 14 percent. Otherwise, an additional source in twilight is indicated. The present results suggest a stratospheric bromine concentration of 16 + or - 4 pptv, a value which is consistent with independent measurements.

Salawitch, Ross J.↗

Temporal and spatial distribution of stratospheric trace gases over Antarctica in August and September, 1987

There have been a large number of suggestions made concerning the origin of the Antarctic 'ozone hole' since its discovery; these changes include stratospheric chemistry, or changes in the solar input, or combinations of these effects. Supporting or refuting these theories requires a wide variety of data for comparison with the predictions. In Aug. and Sept., 1987, a field observation expedition was made over Antarctica from a base in Punta Arenas, Chile. Two aircraft, an ER-2 with in-situ instruments flew at altitudes up to 18 km measuring ozone, water, ClO, BrO, NO sub x, particles, and meteorological parameters in the ozone layer. A DC-8 flew at altitudes of 10 to 12 km, below the ozone layer, using remote sensing instruments for measuring composition and aerosol content of the ozone layer, as well as in-situ instruments for measuring composition at aircraft altitudes. The obsevation of a number of chemical species and their correlation with each other and with meteorological parameters gives a useful set of data for comparison with various theories.

Coffey, M. T.↗

Temporal trends and transport within and around the Antarctic polar vortex during the formation of the 1987 Antarctic ozone hole

During AAOE in 1987 an ER-2 high altitude aircraft made twelve flights out of Punta Arenas, Chile (53 S, 71 W) into the Antarctic polar vortex. The aircraft was fitted with fast response instruments for in situ measurements of many trace species including O3, ClO, BrO, NO sub y, NO, H2O, and N2O. Grab samples of long-lived tracers were also taken and a scanning microwave radiometer measured temperatures above and below the aircraft. Temperature, pressure, and wind measurements were also made on the flight tracks. Most of these flights were flown to 72 S, at a constant potential temperature, followed by a dip to a lower altitude and again assuming a sometimes different potential temperature for the return leg. The potential temperature chosen was 425 K (17 to 18 km) on 12 of the flight legs, and 5 of the flight legs were flown at 450 K (18 to 19 km). The remaining 7 legs of the 12 flights were not flown on constant potential temperature surfaces. Tracer data have been analyzed for temporal trends. Data from the ascents out of Punta Arenas, the constant potential temperature flight legs, and the dips within the vortex are used to compare tracer values inside and outside the vortex, both with respect to constant potential temperature and constant N2O. The time trend during the one-month period of August 23 through September 22, 1987, shows that ozone decreased by 50 percent or more at altitudes form 15 to 19 km. This trend is evident whether analyzed with respect to constant potential temperature or constant N2O. The trend analysis for ozone outside the vortex shows no downward trend during this period. The analysis for N2O at a constant potential temperature indicates no significant trend either inside or outside the vortex; however, a decrease in N2O with an increase in latitude is evident.

Proffitt, M. H.↗