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At least 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

An analysis of the Antarctic Halogen Occultation Experiment trace gas observations

Analysis of the version 16 Halogen Occultation Experiment (HALOE) CH4 data shows that this long-lived trace gas is well correlated with potential vorticity (PV) computed from National Meteorological Center balanced winds. Analyzing late September and October 1992 data, we show that very low CH4 values are confined to the interior of a vortex edge defined by the maximum gradient in PV. The CH4 and HF time tendency is used to estimate the descent rate in the Antarctic vortex. After removing a component of the trend correlated with the HALOE sampling pattern, we compute the lower stratosphere vertical descent rates and net heaing rates in the spring Antarctic vortex. Our computations of the spring Antarctic vortex heating rates give -0.5 to -0.1 K/day. Over the winter season, the overall lower stratospheric descent rate averages about 1.8-1.5 km/month. These computations are in line with radiative transfer estimates of the heating and descent rate. The HALOE data thus appear to be consistent with the picture of an isolated lower stratospheric Antarctic vortex.

Schoeberl, Mark R.↗
NASA NTRS1995

Rate constants and temperature dependences for the reactions of hydroxyl radical with several halogenated methanes, ethanes, and propanes by relative rate measurements

Rate constants of 15 OH reactions with halogen-substituted alkanes, C1 to C3, were studied using a relative rate technique in the temperature range 283-403 K. Compounds studied were CHF2Cl (22), CHF2Br (22B), CH3F (41), CH2F2 (32), CHF3 (23), CHClFCCl2F (122a), CHCl2CF3 (123), CHClFCF3 (124), CH3CF3 (143a), CH3CH2F (161), CF3CHFCF3 (227ea), CF3CH2CF3 (236fa), CF3CHFCHF2 (236ea), and CHF2CF2CH2F (245ca). Using CH4, CH3CCl3, CF3CF2H, and C2H6 as primary reference standards (JPL 92-20 rate constants), absolute rate constants are derived. Results are in good agreement with previous experimental results for six of the compounds studied, including CHF2Cl, CHF2Br, CH2F2, CH3CF3, CHFClCFCl2, and CF3CHFCF3. For the remainder the relative rate constants are lower than those derived from experiments in which OH loss was used to measure the reaction rate. Comparisons of the derived Arrhenius A factors with previous literature transition-state calculations show order of magnitude agreement in most cases. However, the experimental A factors show a much closer proportionality to the number of H atoms in the molecule than is evident from the transition state calculations. For most of the compounds studied, an A factor of (8 +/- 3)E-13 cm(exp 3)/(molecule s) per C-H bond is observed. A new measurement of the ratio k(CH3CCl3)/k(CH4) is reported that is in good agreement with previous data.

Hsu, K.-J.↗
NASA NTRS1996

Scientific Studies in Association with the Halogen Occultation Experiment

This work examines measurements of ozone, NO, NO2, and HCl made by the Halogen Occultation Experiment (HALOE) to track chemical change in the stratosphere. In addition, HALOE observations of two long-lived species, HF and CH4, are used as tracers to distinguish between change due to transport processes and change due to chemistry. The first study investigates the response of NO(x), (NO and NO2) and ozone to the presence of large amounts of sulfate aerosol in the stratosphere following the 1991 eruption of Mount Pinatubo. As the Pinatubo aerosol cleared the atmosphere at 17 mb (about 27-28 km), the partitioning of total reactive nitrogen shifted more toward NO(x), and ozone amounts declined. This trend is opposite that observed at lower altitudes. The second study examines the chemical aftermath of severe ozone depletion over Antarctica in spring. When ozone levels drop to a threshold amount (about 1 ppm near 20 km), the partitioning of the total chlorine family shifts rapidly from reactive species to the reservoir molecule HCl. This sudden repartitioning shuts down further ozone loss and may be significant as filaments of air peel off the polar vortex and mix with mid-latitude air.

Mickley, Lorretta J.↗
NASA NTRS1997

Laboratory Investigations of Stratospheric Halogen Chemistry

A final report for the NASA-supported project on laboratory investigations of stratospheric halogen chemistry is presented. In recent years, this project has focused on three areas of research: (1) kinetic, mechanistic, and thermochemical studies of reactions which produce weakly bound chemical species of atmospheric interest; (2) development of flash photolysis schemes for studying radical-radical reactions of stratospheric interest; and (3) photochemistry studies of interest for understanding stratospheric chemistry. The first section of this paper contains a discussion of work which has not yet been published. All subsequent chapters contain reprints of published papers that acknowledge support from this grant.

Wine, Paul H.↗
NASA NTRS1960

Halogen Containing Gases as Lubricants for Crystallized Glass Ceramic Metal Combinations at Temperatures to 1500 F

Pyroceram 9608 (a crystallized glass ceramic) has been considered for use in high-temperature bearing and seal applications. One of the problems encountered with Pyroceram is the lack of availability of lubricants for the temperature range in which this material becomes practical. Experiments were conducted with Pyroceram sliding on various nickel- and cobalt-base alloys using reactive halogen-containing gases as lubricants. Friction and wear data were obtained as a function of sliding velocity and temperature. Studies were made with a hemispherical rider (3/16-in. rad., Pyroceram 9608) sliding in a circumferential path on the flat surface of a rotating disk (2(1/2) in. diam., nickel- or cobalt-base alloys). The specimens were run in an atmosphere of the various gases with a load of 1200 grams, a sliding velocity of 3200 feet per minute, and temperatures from 75 to 1500 F. The gas CF2Br-CF2Br was found to be an effective lubricant for Pyroceram 9608 sliding on Hastelloy R-235 and Inconel X up to 1400 F. The gas CF2Cl-CF2Cl provided effective lubrication for Pyroceram sliding on various cobalt-base alloys at 1000 F.

Buckley, Donald H.↗
NASA NTRS1999

An Evaluation of the Quality of Halogen Occultation Experiment Ozone Profiles in the Lower Stratosphere

The archived ozone profiles from the Halogen Occultation Experiment (HALOE) have already been corrected for the effects of the spectrally varying, interfering absorption due to aerosols composed of aqueous sulfuric acid, and agreement with correlative measurements in the stratosphere is generally excellent. However, comparisons of sets of coincident HALOE and ozonesonde profiles indicate occasional large differences at the lowest levels of the stratosphere. Most of those instances occur at altitudes just below a well-defined minimum in the 5.26 microns channel aerosol extinction profile, whose wavelength dependence is not represented by a sulfuric acid aerosol model. Further, when the aerosol extinction exceeds about 10(exp 3)/ km, the aerosol correction to the ozone channel transmittances is both large and uncertain. After screening out the HALOE ozone profile segments whose corresponding aerosol/cirrus corrections are likely uncertain and after averaging lie ozonesonde profiles into 2.5 km thick layers, we find that the HALOE ozone areas, on average, to within 10% of their coincident ozonesonde measurements down to 100 hPa at tropical/subtropical latitudes and to 200 hPa at extratropical latitudes. A tightening of the coincidence criteria for the comparisons does not improve the mean differences for the sets nearly as much. Part of the variance of the paired differences was also accounted for when the ozonesonde profile values were integrated into those 2.5 km layers, prior to taking differences. This improvement is due mainly to the vertical averaging of the local, higher-resolution ozonesonde data, matching the lower resolution for HALOE ozone in the lower stratosphere. It is concluded that HALOE is providing accurate ozone profiles throughout the lower stratosphere, when its correction for interfering aerosols has been well characterized and when cirrus layers are not indicated.

Bhatt, Praful P.↗
NASA NTRS2001

Establishing the Dependence of [HO2]/[OH] on Temperature, Halogen Loading, O3, and NO(x) Based on in Situ Measurements from the NASA ER-2

In situ observations of OH and HO2 from the Airborne Southern Hemisphere Ozone Experiment/Measurements for Assessing the Effects of Stratospheric Aircraft (ASHOE/MAESA), Stratospheric TRacers of Atmospheric Transport (STRAT), and Polar Ozone Loss in the Arctic Region in Summer (POLARIS) NASA ER-2 field campaigns are used to examine the partitioning of HO(x) in the lower stratosphere (tropopause to approx.21 km) and upper troposphere (approx.10 km to tropopause). These measurements span a latitude range from 70degS to 90degN and a variety of atmospheric conditions as a result of seasonal changes and altitude. The response of the observed [HO2]/[OH] to changes in temperature, [03], [CO], [NO], [CIO], and [BrO] is investigated. The measured ratio is accurately described (approx.+/-10%) by a steady-state model constrained by the measured mixing ratios of O3, CO, NO, CIO, and BrO, where the model is valid for conditions of HO(x) cycling much faster than HO(x) production and loss. The concentration of HO2 depends on [OH], which, to first order, has been observed to be a simple function of the solar zenith angle in the lower stratosphere. The partitioning between OH and HO2 is controlled by the local chemistry between the HO, radicals and O3, CO, NO, CIO, and BrO. The response of [HO(x)] to changes in [NO(x)] and [O3] is demonstrated. Further observations are necessary to illustrate the response of HO(x) to changes in halogen concentrations. A quantitative understanding of [HO2]/[OH] is important, since many of the reactions that control this ratio are directly involved in catalytic removal of O3 in the lower stratosphere and production of O3 in the upper troposphere.

Lanzendorf, E. J.↗
NASA NTRS1995

Ab Initio Studies of Halogen and Nitrogen Oxide Species of Interest in Stratospheric Chemistry

The ability of modern state-of-the art ab initio quantum chemical techniques to characterize reliably the gas-phase molecular structure, vibrational spectrum, electronic spectrum, and thermal stability of fluorine, chlorine, bromine and nitrogen oxide species will be demonstrated by presentation of some example studies. The ab initio results are shown to be in excellent agreement with the available experimental data, and where the experimental data are either not known or are inconclusive, the theoretical results are shown to fill in the gaps and to resolve experimental controversies. In addition, ab initio studies in which the electronic spectra and the characterization of excited electronic states of halogen oxide species will also be presented. Again where available, the ab initio results are compared to experimental observations, and are used to aid in the interpretation of experimental studies.

Lee, Timothy J.↗
NASA NTRS2004

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.↗
NASA NTRS2009

Retrieval Algorithms for the Halogen Occultation Experiment

The Halogen Occultation Experiment (HALOE) on the Upper Atmosphere Research Satellite (UARS) provided high quality measurements of key middle atmosphere constituents, aerosol characteristics, and temperature for 14 years (1991-2005). This report is an outline of the Level 2 retrieval algorithms, and it also describes the great care that was taken in characterizing the instrument prior to launch and throughout its mission life. It represents an historical record of the techniques used to analyze the data and of the steps that must be considered for the development of a similar experiment for future satellite missions.

Thompson, Robert E.↗
NASA NTRS2009

Trends and Solar Cycle Effects in Temperature Versus Altitude From the Halogen Occultation Experiment for the Mesosphere and Upper Stratosphere

Fourteen-year time series of mesospheric and upper stratospheric temperatures from the Halogen Occultation Experiment (HALOE) are analyzed and reported. The data have been binned according to ten-degree wide latitude zones from 40S to 40N and at 10 altitudes from 43 to 80 km-a total of 90 separate time series. Multiple linear regression (MLR) analysis techniques have been applied to those time series. This study focuses on resolving their 11-yr solar cycle (or SC-like) responses and their linear trend terms. Findings for T(z) from HALOE are compared directly with published results from ground-based Rayleigh lidar and rocketsonde measurements. SC-like responses from HALOE compare well with those from lidar station data at low latitudes. The cooling trends from HALOE also agree reasonably well with those from the lidar data for the concurrent decade. Cooling trends of the lower mesosphere from HALOE are not as large as those from rocketsondes and from lidar station time series of the previous two decades, presumably because the changes in the upper stratospheric ozone were near zero during the HALOE time period and did not affect those trends.

Remsberg, Ellis E.↗
NASA NTRS2008

On the Response of Halogen Occultation Experiment (HALOE) Stratospheric Oxone and Temperature to the 11-yr Solar Cycle Forcing

Results are presented on responses in 14-yr time series of stratospheric ozone and temperature from the Halogen Occultation Experiment (HALOE) of the Upper Atmosphere Research Satellite (UARS) to a solar cycle (SC-like) variation. The ozone time series are for ten, 20-degree wide, latitude bins from 45S to 45N and for thirteen "half-Umkehr" layers of about 2.5 km thickness and extending from 63 hPa to 0.7 hPa. The temperature time series analyses were restricted to pressure levels in the range of 2 hPa to 0.7 hPa. Multiple linear regression (MLR) techniques were applied to each of the 130 time series of zonally-averaged, sunrise plus sunset ozone points over that latitude/pressure domain. A simple, 11-yr periodic term and a linear trend term were added to the final MLR models after their seasonal and interannual terms had been determined. Where the amplitudes of the 11-yr terms were significant, they were in-phase with those of the more standard proxies for the solar uv-flux. The max minus min response for ozone is of order 2 to 3% from about 2 to 5 hPa and for the latitudes of 45S to 45N. There is also a significant max minus min response of order 1 K for temperature between 15S and 15N and from 2 to 0.7 hPa. The associated linear trends for ozone are near zero in the upper stratosphere. Negative ozone trends of 4 to 6%/decade were found at 10 to 20 hPa across the low to middle latitudes of both hemispheres. It is concluded that the analyzed responses from the HALOE data are of good quality and can be used to evaluate the responses of climate/chemistry models to a solar cycle forcing.

Remsberg, E. E.↗
DOE OSTI2024

Biosynthesis of Strained Amino Acids by a PLP‐Dependent Enzyme through Cryptic Halogenation

Abstract Amino acids (AAs) are modular building blocks which nature uses to synthesize both macromolecules, such as proteins, and small molecule natural products, such as alkaloids and non‐ribosomal peptides. While the 20 main proteinogenic AAs display relatively limited side chain diversity, a wide range of non‐canonical amino acids (ncAAs) exist that are not used by the ribosome for protein synthesis, but contain a broad array of structural features and functional groups. In this communication, we report the discovery of the biosynthetic pathway for a new ncAA, pazamine, which contains a cyclopropane ring formed in two steps. In the first step, a chlorine is added onto the C 4 position of lysine by a radical halogenase, PazA. The cyclopropane ring is then formed in the next step by a pyridoxal‐5′‐phosphate‐dependent enzyme, PazB, via an S N 2‐like attack at C 4 to eliminate chloride. Genetic studies of this pathway in the native host, Pseudomonas azotoformans , show that pazamine potentially inhibits ethylene biosynthesis in growing plants based on alterations in the root phenotype of Arabidopsis thaliana seedlings. We further show that PazB can be utilized to make an alternative cyclobutane‐containing AA. These discoveries may lead to advances in biocatalytic production of specialty chemicals and agricultural biotechnology.

Sosa, Max B.↗