Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “BrO”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Ozone and nitrogen dioxide ground based monitoring by zenith sky visible spectrometry in Arctic and Antarctic

Unattended diode array spectrometers have been designed for ground based stratospheric trace species monitoring by zenith sky visible spectrometry. Measurements are performed with a 1.0 nm resolution between 290 nm and 590 nm in order to allow simultaneous evaluations of column densities of ozone, nitrogen dioxide. Field tests have shown that the species can be monitored with a precision of + or - 2 Dobson for the first and + or - 2.10 to the 15th mol/sq cm for the second, although the absolute accuracy of the method is limited by the error of the estimation of the atmospheric optical path of the scattered light. Two identical instruments were set up in January 1988, one in Antarctica at Dumont d'Urville (66 S, 140 E) to be operated all year and another one in the Arctic at ESRANGE at Kiruna (68 N; 22 E) which will operate to the final warming of spring 1988. The data are processed in real time at both stations. O3 and NO2 columns are transmitted together with surface and stratospheric temperature and winds. They are also recorded for further treatment and search for OClO and BrO. Only one month of data from Antarctica is available at the moment. Obtained during polar summer, they cannot show more than stable columns of O3 and NO2 and for the last species, the buildup of its diurnal variation.

Pommereau, J. P.↗
NASA NTRS1988

Measurements of the ClO radical vibrational band intensity and the ClO + ClO + M reaction product

There is considerable interest in the kinetics and concentrations of free radicals in the stratosphere. Chlorine monoxide is a critically important radical because of its role in catalytic cycles for ozone depletion. Depletion occurs under a wide variety of conditions including the Antarctic spring when unusual mechanisms such as the BrO sub x/ClO sub x, ClO dimer (Cl sub 2 O sub 2), and ClO sub x/HO sub x cycles are suggested to operate. Infrared spectroscopy is one of the methods used to measure ClO in the stratosphere (Menzies 1979 and 1983; Mumma et al., 1983). To aid the quantification of such infrared measurements, researchers measured the ClO ground state fundamental band intensity.

Burkholder, James B.↗
NASA NTRS1988

Modelling the Antarctic lower stratosphere

Results form modeling studies of the Antarctic lower stratosphere which have attempted to simulate the large springtime ozone losses and corresponding changes in other trace constituents are given. These studies were carried out in a photochemical box model, a one-dimensional model without transport and in a two-dimensional photochemical-dynamical-radiation model. The photochemical studies have investigated inter alia the sensitivity of ozone to inclusion in the model of heterogeneous chemistry, and to the inclusion of the ClO dimer. When both of these are incorporated in the model, ozone depletions resembling whose found in Halley Bay in 1987 (J.C. Farman, Nature, 329, 1987) can be reproduced. The temporal variations (both diurnal and during the August to October period) of a number of important tracers including HCl, ClONO2, OClO and BrO are discussed. The two-dimensional study concentrated on the difficulty of establishing in the model the dynamical preconditioning of the lower polar stratosphere - low temperatures, low N2O, etc., high ClOx. Calculations are presented to show: (1) the depletion of ozone during the springtime season, (2) the effect of large ozone losses on lower latitudes, and (3) the longer term (multi-year) variations of ozone in Antarctica, assuming realistic increases in the atmospheric halogen burden.

Chipperfield, M. P.↗
NASA NTRS1990

Description of SAFIRE for ISES

The SAFIRE (Spectroscopy of the Atmosphere using Far Infrared Emission) is a limb emission experiment using a far-IR Fourier transform spectrometer (FTS) and a mid-IR broadband multispectral radiometer covering the range 80 to 1600/cm. The purpose of this experiment is to obtain vertical distributions of temperature and key constituents of O(y), HO(y), NO(y), ClO(y), and BrO(y) families in the stratosphere, mesosphere, and thermosphere. The spectral channels and gases within each channel are summarized. The instrument includes a 48 element (6 x 8) Ge:GA detector array operating at 4 K in the far-IR and a 105 element (7 x 15) HgCdTe array operating at 80 K in the mid-IR. The SAFIRE uses four different scan modes for vertical coverage and resolution to address various scientific requirements. The SAFIRE data reduction will start with the retrieval of temperature profile as a function of pressure using two CO2 channel data. Constituent distributions then are obtained from other channel data using the retrieved temperature profile. The SAFIRE measurements are limited to the region above the tropopause because of radiance saturation by H2O and clouds. The computational capability necessary to process at the instrument data rate is estimated to be 19 MFLOPS for FTS data and 0.02 MFLOPS for radiometer data. It seems, therefore, that the real-time applications of SAFIRE data using an onboard processing device is not feasible. Although a temperature anomaly may be detected from the two CO2 radiometer channels using an onboard processor for the stratosphere, it is not possible to distinguish between CO2 outflux and temperature anomaly. Temperature anomaly does not, therefore, offer tropospheric information useful for real-time application.

Park, Jae H.↗
NASA NTRS1989

Implications of AAOE observations for proposed chemical explanations of the seasonal and interannual behavior of Antarctic ozone

Model simulations were used to investigate the seasonal and interannual behavior of ozone for different choices of initial odd nitrogen concentration in July and different assumptions on the heterogeneous reactions, with particular consideration given to the possible contribution of chlorine chemistry to the ozone hole phenomenon. The numerical experiments were selected based on the simulations of the observed trace gas concentrations during the Airborne Antarctic Ozone Experiment in 1987. In all cases considered, the catalytic cycle associated with the formation and photolysis of Cl2O2 could account for more than half of the photochemical removal of O3 within the Antarctic vortex through mid-September. The reaction of BrO with ClO, which accounts for 15-20 percent of O3 removal in the same period, tends to play a more important role toward the end of September, when the concentration of ClO is expected to decrease. No simple relationship was found between the increase in chlorine lavel and the interannual decrease in Antarctic O3.

Ko, M. K. W.↗
NASA NTRS1989

Stratospheric ozone - Impact of human activity

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Mcelroy, Michael B.↗
NASA NTRS1990

Loss of ozone in the Arctic vortex for the winter of 1989

Measurements of ClO (Brune et al., 1990) acquired during the Airborne Arctic Stratospheric Expedition are used to infer concentrations of reactive chlorine (ClO + 2 x Cl2O2). Observed fields of potential temperature and potential vorticity are used to extrapolate in situ data to larger regions of the vortex. Calculated values of the loss rate of O3, based on estimates of reactive chlorine and measurements of BrO (Toohey et al., 1990), suggest that the loss of O3 was abut 12 pct for levels of the atmosphere with potential temperatures between 440 and 470 K over the 39 day duration of the ER-2 flights into the polar vortex. Calculated loss rates agree with observed rates of removal of O3, although significant uncertainties exist for each.

Salawitch, Ross J.↗
NASA NTRS1991

An overview of the spectroscopy of the atmosphere using far infrared emission experiment (SAFIRE)

The SAFIRE experiment was conceived to satisfy a long-standing need for simultaneous middle atmosphere observations of ozone and important O(y), HO(y), NO(y), ClO(y), and BrO(y) gases, coupled with dynamics data. This will be accomplished using interferometry and broadband radiometry to sound the Earth limb in the far IR and mid IR, respectively. The experiment will employ the latest developments in detector and cryogenic cooling technology in order to achieve the measurement objectives. Detailed instrument and simulated atmospheric retrieval studies show that important gases such as OH, HO2, H2O2, HDO, N2O5, and HOCl can be observed with good accuracy.

Russell, James M., III↗
NASA NTRS1994

The 1990 vertical distribution of two important halons (F-12B1 and F-13B1) in the tropics

The first vertical profiles of F-12B1 and F-13B1 had been obtained in the tropical troposphere and stratosphere by us in 1987. The measurement of these substances responsible for almost the entire anthropogenic contribution to the stratospheric BrO(x) budget is important in the tropics, as tropical upwelling provides their injection along with that of other pollutants, into the stratosphere. To ascertain the trends of these distributions and foster the data, the 1987 experiment was repeated in April 1990. Like 1987, the MPAE cryogenic whole air sampler was launched on a balloon from Hyderabad, India (17.5 deg N), and 14 samples were collected between 10 and 35 km altitude. The results obtained by means of GC and GC-MS analyses showed that the atmospheric abundance of both F-12B1 and F-13B1 is increasing at a fast rate, respectively by about 15 percent and 10 percent per year. From 1987 to 1990, F-12B1 and F-13B1 tropospheric mixing ratios have been growing from 1.2 and 1.3 ppt to 1.8 and 1.7 ppt, respectively. The vertical profiles will be discussed.

Singh, O. N.↗
NASA NTRS1994

Are models of catalytic removal of O3 by HO(x) accurate? Constraints from in situ measurements of the OH to HO2 ratio

Measurements of the ratio OH/HO2, NO, O3, ClO, and BrO were obtained at altitudes from 15-20 km and latitudes from 15-60 deg N. A method is presented for interpreting the rates of chemical transformations that (1) are responsible for over half the ozone removal rate in the lower stratosphere via reactions of HO2; and (2) control the abundance of HO2 through coupling to nitrogen and halogen radicals. The results show our understanding of the chemical reactions controlling the partitioning of OH and HO2 is complete and accurate and that the potential effects of 'missing chemistry' are strickly constrained in the region of the atmosphere encompassed by the observations. The analysis demonstrates that the sensitivity of the ratio OH/HO2 to changes in NO is described to within 12% by current models. This reduces by more than a factor of 2 the effect of uncertainty in the coupling of hydrogen and nitrogen radicals on the analysis of the potential effects of perturbations to odd notrogen in the lower statosphere.

Cohen, R. C.↗
NASA NTRS1994

A new numerical model of the middle atmosphere. 2: Ozone and related species

A new two-dimensional model with detailed photochemistry is presented. The model includes descriptions of planetary wave and gravity wave propagation and dissipation to characterize the wave forcing and associated mixing in the stratosphere and mesosphere. Such a representation allows for explicit calculation of the regions of strong mixing in the middle atmosphere required for accurate simulation of trace gas transport. The new model also includes a detailed description of photochemical processes in the stratosphere and mesosphere. The downward transport of H2, H2O, and NO(y) from the mesosphere to the stratosphere is examined, and it is shown that mesospheric processes can influence the distributions of these chemical species in polar regions. For HNO3 we also find that small concentrations of liquid aerosols above 30 km could play a major role in determining the abundance in polar winter at high latitudes. The model is also used to examine the chemical budget of ozone in the midlatitude stratosphere and to set constraints on the effectiveness of bromine relative to chlorine for ozone loss and the role of the HO2 + BrO reaction. Recent laboratory data used in this modeling study suggest that this process greatly enhances the effectiveness of bromine for ozone destruction, making bromine-catalyzed chemistry second only to HO(x)-catalyzed ozone destruction in the contemporary stratosphere at midlatitudes below about 18 km. The calculated vertical distribution of ozone in the lower stratosphere agrees well with observations, as does the total column ozone during most seasons and latitudes, with the important exception of southern hemisphere winter and spring.

Garcia, Rolando R.↗
NASA NTRS1995

The reaction O((3)P) + HOBr: Temperature dependence of the rate constant and importance of the reaction as an HOBr stratospheric loss process

The absolute rate constant for the reaction O((3)P) + HOBr has been measured between T = 233K and 423K using the discharge-flow kinetic technique coupled to mass spectrometric detection. The value of the rate coefficient at room temperature is (2.5 +/- 0.6) x 10(exp -11)cu cm/molecule/s and the derived Arrhenius expression is (1.4 +/- 0.5) x 10(exp -10) exp((-430 +/- 260)/T)cu cm/molecule/s. From these rate data the atmospheric lifetime of HOBr with respect to reaction with O((3)P) is about 0.6h at z = 25 km which is comparable to the photolysis lifetime based on recent measurements of the UV cross section for HOBr. Implications for HOBr loss in the stratosphere have been tested using a 1D photochemical box model. With the inclusion of the rate parameters and products for the O + HOBr reaction, calculated concentration profiles of BrO increase by up to 33% around z = 35 km. This result indicates that the inclusion of the O + HOBr reaction in global atmospheric chemistry models may have an impact on bromine partitioning in the middle atmosphere.

Nesbitt, F. L.↗
NASA NTRS1997

Kinetics of the Reactions of IO Radicals with NO and NO2

A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

Daykin, E. P.↗
NASA NTRS1997

Kinetics of the Reactions of Cl((sup 2)P(sub J)) and Br((sup 2)P(sub 3/2)) with O3

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of the important stratospheric reactions Cl((sup 2)P(sub J)) + O3 yields ClO + O2 and Br((sup 2)P(sub 3/2)) + O3 yields BrO + O2 as a function of temperature. The temperature dependence observed for the Cl((sup 2)P(sub J)) + O3 reaction is nonArrhenius, but can be adequately described by the following two Arrhenius expressions (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 1)(T) = (1.19 +/- 0.21) x 10(exp -11) exp[(-33 +/- 37)/T] for T = 189-269 K and k(sub 1)(T) = (2.49 +/- 0.38) x 10(exp -11) exp[(-233 +/- 46)/T] for 269-385 K. At temperatures below 230 K, the rate coefficients determined in this study are faster than any reported previously. Incorporation of our values for k(sub 1)(T) into stratospheric models would increase calculated ClO levels and decrease calculated HCI levels; hence the calculated efficiency of ClO catalyzed ozone destruction would increase. The temperature dependence observed for the Br((sup 2)P(sub 3/2)) + O3 reaction is adequately described by the following Arrhenius expression (units are cu cm/(molecule.s), errors are 2 sigma and represent precision only): k(sub 2)(T) = (1.50 +/- 0.16) x 10(exp -11)exp[(-775 +/- 30)/T for 195-392 K. While not in quantitative agreement with Arrhenius parameters reported in most previous studies, our results almost exactly reproduce the average of all earlier studies and therefore will not affect the choice of k(sub 2)(T) for use in modeling stratospheric BrO2 chemistry.

Nicovich, J. M.↗
NASA NTRS1997

Kinetics of the Reactions of O((sup 3)P) and Cl((sup 2)P) with HBr and Br2

A laser flash photolysis-resonance fluorescence technique has been employed to study the kinetics of reactions (1)-(4) as a function of temperature. (1) O((sup 3)P) + Br2 yields BrO + Br((sup 2)P(sub 3/2)) at 255-350 K; (2) Cl((sup 2)P) + Br2 yields BrCl + Br((sup 2)P(sub 3/2)) at 298-401 K; (3) O((sup 3)P) + HBr yields OH + Br((sup 2)P(sub J)) at 250-402 K; (4) Cl((sup 2)P) + HBr yields HCl + Br((sup 2)P(sub J)) at 257-404 K. In all cases, the concentration of the excess reagent, i.e, HBr or Br2, was measured in situ in the slow flow system by UV-visible photometry. Heterogeneous dark reactions between XBr (X equals H or Br) and the photolytic precursors for Cl((sup 2)P) and O((sup 3)P) (Cl2 and O3, respectively) were avoided by injecting minimal amounts of precursor into the reaction mixture immediately upstream from the reaction zone. The following Arrhenius expressions summarize our results (errors are 2 sigma and represent precision only, units are cu cm/(molecule.s): k(sub 1) = (1.76 +/- 0.80) x 10(exp -11 exp[(40 +/- 100)/T]; k(sub 2) = (2.40 +/- 1.25) x 12(exp -10) exp[-(144 +/- 176)/T]; k(sub 3) = (5.11 +/- 2.82) x 10(exp -12) exp[-(1450 +/- 160)/T]; k(sub 4) = (2.25 +/- 0.56) x 10(exp -11) exp[-(400 +/- 80)/T]. The consistency (or lack thereof) of our results with those reported in previous kinetics and dynamics studies of reactions (1)-(4) is discussed.

Nicovich, J. M.↗
NASA NTRS1998

Tropospheric- Stratospheric Measurement Studies Summary

The two high altitude aircraft, ER-2 NASA #706 and 709 and the DC-8 NASA #717 are in active use in several programs of upper atmospheric research to study polar ozone changes, stratospheric-tropospheric exchange processes and atmospheric effects of aviation aircraft. The ER-2 has participated in seven major missions which mainly concentrated on vortex dynamics and the large losses of Ozone in the Polar regions (Ozone hole) observed in the spring. One mission verified the complex dynamical chemical and physical processes that occur during sunrise and sunset. Stratospheric Tracers of Atmospheric Transport (STRAT) obtained background measurements using the full ER-2 suite of instruments. Photochemistry of Ozone Loss in the Arctic Region in Summer (POLARIS) in 1997 assisted in understanding the mid-latitude and Arctic Ozone losses during the Northern Summer. The DC-8 with the Meteorological Measurement System (MMS) has participated in the Subsonic Aircraft: Cloud and Contrail Effects Special Study (SUCCESS), in 1996 and the Subsonic assessment Ozone and Nitrogen oxide experiment (SONEX) in 1997 missions. The MMS with its sophisticated software accurately measures ground speed and attitude, in-situ static and dynamic pressure total temperature, which are used to calculate the three dimensional wind fields, static pressure, temperature and turbulence values to meteorological accuracy. The meteorological data is not only of interest for its own sake in atmospheric dynamical processes such as mountain waves and flux measurements; but is also required by other ER-2 experiments that simultaneously measure water vapor, O3, aerosols, NO, HCl, CH4, N2O, ClO, BrO, CO2, NOy, HOx and temperature gradients. MMS products are extensively used to assist in the interpretation of their results in understanding the importance of convective effects relative to in-situ chemical changes, as may be noted by examining the list of references attached. The MMS consists of three subsystems: (a) aircraft instrumentation, inertial navigation system (INS), static and dynamic pressure taps, (b) additional dedicated instrumentation measuring angle of attack, yaw, total temperature, and a GPS which on the DC-8 measures position, velocity and attitude (c) an on board data, storage and computing acquisition system. This instrumentation and the associated software requires both an on-going laboratory ground calibration procedure for the total air temperature, static and total pressure inputs, verification of the INS dynamic response and also extensive air measurements and intercomparisons which ultimately verify and calibrate the complete system and its software. More than the usual accuracy is required because of the near cancellation occurring in the difference between the ground speed and true airspeed vectors used to give the wind vector. In the past year we have redesigned, recalibrated and used the MMS system on the NASA DC-8 that was previously used in the SUCCESS mission for the SONEX mission. Two papers were co-authored based on SUCCESS flights. Several reports and handouts were written for SONEX. Calibrations of the DC-8 pressure transducer temperature measuring thermistors was completed and an extensive analysis spanning several years of data files of the DC-8 Rosemount pressure transducer calibrations was done.

Browen, Stuart W.↗
NASA NTRS2000

Modeling Stratospheric Constituents: Reactive Species That Regulate Ozone

Photochemical loss of stratospheric ozone occurs primarily by catalytic cycles whose rates are limited by the concentration of OH, HO2, NO2, ClO, and/or BrO as well as the concentration of either atomic oxygen or of ozone itself. Once the concentrations of these gases are established, the photochemical loss rate of O3 depends on the rate coefficient of only a handful of key reactions. We have developed a method for testing our understanding of stratospheric ozone photochemistry by comparing measured and modeled concentrations of reactive hydrogen, nitrogen, chlorine and bromine radicals using a photochemical steady state model constrained by observed concentrations of long-lived precursors (e.g., NO(y), Cl(y), Br(y), O3, H2O, CH4) and environmental parameters such as ozone column, reflectivity, and aerosol surface area. We will show based on analyses of observations obtained by aircraft, balloon, and satellite platforms during the POLARIS campaign that our overall understanding of the processes that regulate these radical species is very good. The most notable current discrepancies are the tendency to underestimate observed NO2 by 15 to 30% for air masses that experience near continuous solar illumination over a 24 hour period and the tendency to underestimate observed OH and H02 by about 10 to 20% during midday and by much larger amounts at high solar zenith angle (SZA > 85). Possible resolutions to these discrepancies will be discussed. This study was carried out in close collaboration with many members of the POLARIS science team.

Salawitch, Ross J.↗
NASA NTRS2000

Heat of Formation of OBrO: An Experiment Photoionization Study

The potential importance of OBrO in atmospheric chemistry has been suggested recently. Although there appear to be no experimental measurements of deltaH(OBrO), estimated values range from 70 to 152 kJ/mol. In the present investigation, the appearance energy (AE) of BrO+ from OBrO was measured by employing a discharge flow-photoionization mass spectrometer that is operated at beamline U-11. The heat of formation was derived from the AE result and the ionization energy of OBrO [IE = 10.29 eV]. The AE experiments yield a threshold at about 98.7 nm that gives, in turn, a value for AH(OBrO) of 180 +/- 10 kJ/mol. The difference with the estimated values mentioned above and the concomitant implications for the atmospheric reactions of OBrO will be discussed.

Klemm, R. Bruce↗