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At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS1989

Three dimensional simulation of spatial and temporal variability of stratospheric hydrogen chloride

Spatial and temporal variability of atmospheric HCl columns are calculated for January 1979 using a three-dimensional chemistry-transport model designed to provide the best possible representation of stratospheric transport. Large spatial and temporal variability of the HCl columns is shown to be correlated with lower stratospheric potential vorticity and thus to be of dynamical origin. Systematic longitudinal structure is correlated with planetary wave structure. These results can help place spatially and temporally isolated column and profile measurements in a regional and/or global perspective.

Kaye, Jack A.↗
NASA NTRS1990

The deep atmosphere of Venus revealed by high-resolution nightside spectra

The first high-resolution spectroscopic observations of the night side of Venus obtained in two narrow spectral windows centered at 1.74 and 2.3 microns, where the nightside is anomalously bright, are reported. Absorption features from CO2, CO, H2O, HDO, HCl, HF, and COS are detected, and there are a number of unidentified features. A preliminary analysis indicates that the observed radiation is thermal emission from atmospheric layers in the eight-bar pressure region for the 2.3 micron window and even deeper at 1.7 micron. The derived CO and H2O abundances agree with in situ Pioneer measurements in the deep troposphere and are consistent with the high deuterium enrichment inferred from Pioneer data. The first measurements of HCl and HF below the clouds are reported along with the first firm detection of COS.

Bezard, Bruno↗
NASA NTRS1991

Recovery of precious metals from space

The overall objective is to develop efficient and economical separation and recovery methods for the platinum group and other precious metals. The separation of Pd(II) from Pt(II), Ir(III), and Rh(III) with trioctylphosphine oxide (TOPO) in heptane using centrifugal partition chromatography (CPC) was investigated. Activities to achieve this objective focussed on selection and evaluation of extraction systems for the PGM and modification of selected systems for multistage operation with a view to scaling up to desired macro levels. On the basis of preliminary evaluation of a series of simple metal complexing agents and chelating agents, the TOPO in heptane was selected as a likely system for isolating of Pd(II) and Pt(II) from the other PGM. A multistage apparatus capable of configuration as a simple rugged device, a centrifugal partition chromatograph (CPC), was shown to be effective. The extraction of Pd(II) was studied by CPC and batch solvent extraction. The distribution ratios for Pd(II) determined by both methods agree well. In low HCl concentrations (less than 0.1 M), the extracted species was PdCl2.(TOPO)2, irrespective of the chloride concentration, while at acid concentrations above 0.1 M, the Pd was extracted as the ion pair, 2(TOPO.H+).(PdCl4)2-. Base line separation of Pd(II) and Pt(II) in CPC was obtained under a variety of chloride and HCl concentration. It was demonstrated that the efficiency of CPC for metal separation was limited by chemical kinetic factors rather than instrumental factors, strongly suggesting that dramatic improvements can be achieved by studying reaction kinetics of formation and dissociation of the extractable metal complex.

Freiser, Henry↗
NASA NTRS1989

Proposed reference models for CO2 and halogenated hydrocarbons

The vertical distribution of carbon dioxide, halocarbons and their sink products, HCl and HF, have become available, mainly by means of balloon measurements. Most measurements were made at northern mid-latutudes, but some constituents were measured at tropical latitudes and in the Southern Hemisphere as well. An attempt is made here to combine the available data for presentation of reference models for CO2, CCl4 CCl3F, CCl2F2, CClF3, CF4, CCl2F-CClF2, CClF2-CClF2, CClF2-CF3, CF3-CF3, CH3Cl, CHClF2, CH3-CCl3, CBrClF2, CBrF3, HCl and HF.

Fabian, P.↗
NASA NTRS1991

Inferring the abundances of ClO and HO2 from Spacelab 3 atmospheric trace molecule spectroscopy observations

The vertical distributions of the important highly reactive stratospheric species, ClO and HO2, have been inferred from Spacelab 3 (May 1985) Atmospheric Trace Molecule Spectroscopy (ATMOS) measurements of more detectable radical and reservoir species. A simple steady state algebraic expression for ClO, utilizing the observed ClONO2/NO2 abundance ratio, approximates the ClO results of a time-dependent photochemical model at sunset (30 deg N). Balloon measurements of ClO and comparisons of time-dependent photochemical model calculations of ClONO2 and HCl with the corresponding ATMOS profiles suggest that the actual ClO values are less than the time-dependent model profiles for ClO at sunset and sunrise (47 deg S). Errors in the current model simulation of the partitioning among the principal free chlorine species (HCl, ClONO2, and ClO) are indicated. The accuracy of the time-dependent model calculations of HO2 is suggested by the agreement between model results and ATMOS observations for HO2NO2 and balloon measurements of HO2. This confirms for the first time the procedure suggested previously by a number of authors of deriving HO(x) abundances from observed fields of O3 and H2O.

Allen, Mark↗
NASA NTRS1991

Heterogeneous reactions with NaCl in the El Chichon volcanic aerosols

Previous investigations of the effects of the 1982 eruption of the El Chichon volcano could not explain all the observations of changes in O3, HCl, NO and NO2 simultaneously without proposing unproven chemical reactions. Since reactions between solid NaCl and gaseous ClNO3 and N2O5 rapidly produce photochemically active chlorine species and solid NaNO3 in laboratory experiments, it is suggested that these reactions could have occurred with the NaCl observed to be present in the El Chichon sulfuric acid areosols. As a consequence, it is predicted that HCl should increase substantially, while NO(x) should decrease, in agreement with the measurements after the eruption. Ozone should be only slightly affected by these reactions. Reactions between solid NaCl and the acids H2SO4 and HNO3 might prove to be important, but sufficient evidence regarding their efficiency and the pressure of HNO3 in the aerosols is lacking.

Michelangeli, Diane V.↗
NASA NTRS1991

Application of physical adsorption thermodynamics to heterogeneous chemistry on polar stratospheric clouds

Laboratory isotherms for the binding of several nonheterogeneously active atmospheric gases and for HCl to water ice are translated into adsorptive equilibrium constants and surface enthalpies. Extrapolation to polar conditions through the Clausius Clapeyron relation yields coverage estimates below the percent level for N2, Ar, CO2, and CO, suggesting that the crystal faces of type II stratospheric cloud particles may be regarded as clean with respect to these species. For HCl, and perhaps HF and HNO3, estimates rise to several percent, and the adsorbed layer may offer acid or proton sources alternate to the bulk solid for heterogeneous reactions with stratospheric nitrates. Measurements are lacking for many key atmospheric molecules on water ice, and almost entirely for nitric acid trihydrate as substrate. Adsorptive equilibria enter into gas to particle mass flux descriptions, and the binding energy determines rates for desorption of, and encounter between, potential surface reactants.

Elliott, Scott↗
NASA NTRS1991

X-ray photoelectron spectroscopy study of chemically-etched Nd-Ce-Cu-O surfaces

Acetic acid, Br2, and HCl solutions are investigated for removing insulating species from Nd(1.85)Ce(0.15)CuO(4-delta) (NCCO) thin film surfaces. X-ray photoelectron spectroscopy (XPS) shows that the HCl etch is most effective, yielding O 1s spectra comparable to those obtained from samples cleaned in vacuum and a clear Fermi edge in the valence band region. Reduction and oxidation reversibly induces and eliminates, respectively, Fermi level states for undoped samples, but has no clearly observable effect on the XPS spectra for doped samples. Reactivity to air is much less for NCCO compared to hole superconductors, which is attributed to the lack of reactive alkaline earth elements in NCCO.

Vasquez, R. P.↗
NASA NTRS1990

Quantification of hydrochloric acid and particulate deposition resulting from Space Shuttle launches at John F. Kennedy Space Center, Florida, U.S.A.

Results are presented from studies designed to identify deposition patterns and quantify the ecosystem loading rates of exhaust constituents (which are primarily Al2O3 and HCl) from the Space Shuttle solid rocket motors in the area of the Kennedy Space Center launch pad. Results of measurements indicate that, under certain meteorological conditions, as much as 7.1 x 10 exp 3 kg of particulates and 3.4 x 10 exp 3 kg HCL can be deposited to the near-field environment beyond the launch pad perimeter fence during one STS launch.

Dreschel, Thomas W.↗
NASA NTRS1992

Anodic etching of p-type cubic silicon carbide

p-Type cubic silicon carbide was anodically etched using an electrolyte of HF:HCl:H2O. The etching depth was determined versus time with a fixed current density of 96.4 mA/sq cm. It was found that the etching was very smooth and very uniform. An etch rate of 22.7 nm/s was obtained in a 1:1:50 HF:HCl:H2O electrolyte.

Harris, G. L.↗
NASA NTRS1991

Heterogeneous processes: Laboratory, field, and modeling studies

The efficiencies of chemical families such as ClO(x) and NO(x) for altering the total abundance and distribution of stratospheric ozone are controlled by a partitioning between reactive (active) and nonreactive (reservoir) compounds within each family. Gas phase thermodynamics, photochemistry, and kinetics would dictate, for example, that only about 1 percent of the chlorine resident in the lower stratosphere would be in the form of active Cl or ClO, the remainder existing in the reservoir compounds HCl and ClONO2. The consistency of this picture was recently challenged by the recognition that important chemical transformations take place on polar regions: the Airborne Antarctic Ozone Experiment (AAOE) and the Airborne Arctic Stratospheric Expedition (AASA). Following the discovery of the Antarctic ozone hole, Solomon et al. suggested that the heterogeneous chemical reaction: ClONO2(g)+HCl(s) yields Cl2(g)+HNO3(s) could play a key role in converting chlorine from inactive forms into a species (Cl2) that would rapidly dissociate in sunlight to liberate atomic chlorine and initiate ozone depletion. The symbols (s) and (g) denote solid phase, or adsorbed onto a solid surface, and gas phase, respectively, and represent the approach by which such a reaction is modeled rather than the microscopic details of the reaction. The reaction was expected to be most important at altitudes where PSC's were most prevalent (10 to 25 km), thereby extending the altitude range over which chlorine compounds can efficiently destroy ozone from the 35 to 45 km region (where concentrations of active chlorine are usually highest) to lower altitudes where the ozone concentration is at its peak. This chapter will briefly review the current state of knowledge of heterogeneous processes in the stratosphere, emphasizing those results obtained since the World Meteorological Organization (WMO) conference. Sections are included on laboratory investigations of heterogeneous reactions, the characteristics and climatology of PSC's, stratospheric sulfate aerosols, and evidence of heterogeneous chemical processing.

Poole, Lamont R.↗
NASA NTRS1993

Predicting ground level impacts of solid rocket motor testing

Beginning in August of 1988 and continuing until the present, NASA at Stennis Space Center, Mississippi has conducted environmental monitoring of selected static test firings of the solid rocket motor used on the Space Shuttle. The purpose of the study was to assess the modeling protocol adapted for use in predicting plume behavior for the Advanced Solid Rocket Motor that is to be tested in Mississippi beginning in the mid-1990's. Both motors use an aluminum/ammonium perchlorate fuel that produces HCl and Al2O3 particulates as the major combustion products of concern. A combination of COMBUS.sr and PRISE.sr subroutines and the INPUFF model are used to predict the centerline stabilization height, the maximum concentration of HCl and Al2O3 at ground level, and distance to maximum concentration. Ground studies were conducted to evaluate the ability of the model to make these predictions. The modeling protocol was found to be conservative in the prediction of plume stabilization height and in the concentrations of the two emission products predicted.

Douglas, Willard L.↗
NASA NTRS1993

Chlorine catalyzed destruction of ozone - Implications for ozone variability in the upper stratosphere

The annual mean and the annual amplitude of ozone have been derived from ozone measurements from the SBUV and SBUV/2 spectrometers on board the Nimbus-7 and NOAA-11 satellites. These values differ significantly from values calculated using a two-dimensional model of stratospheric photochemistry and dynamics with standard chemistry. We have found that the differences between the calculated and data-derived values are considerably improved by changing the partitioning in the Cly family to create a larger reservoir of HCl and reducing ClO. This is accomplished by including a channel for the products HCl + O2 from the reaction ClO + OH in addition to the products Cl + HO2. This partitioning also improves the agreement between the calculated and measured values of ClO/HCl ratio.

Chandra, Sushil↗
NASA NTRS1991

Heterogeneous reactions of chlorine nitrate and hydrogen chloride on type I polar stratospheric clouds

A fast-flow reactor coupled with a quadrupole mass spectrometer was used to study the heterogeneous reactions ClONO2 + HCl yields Cl2 + HNO3 (1) and ClONO2 + H2O yields HOCl + HNO3 (2) on vapor-deposited HNO3-H2O ice substrates. It was found that the sticking coefficient of HCl on these substrates was a strong function of the substrate composition, ranging from about 2 x 10 exp -5 at nitric acid trihydrate composition to 6 x 10 exp -3 at 45 wt pct HNO3. The HNO3-H2O ice substrates were found to have large internal surface areas, and corrections for gas-phase diffusion within the porous ices were applied to observed loss rates.

Leu, Ming-Taun↗
NASA NTRS1993

The Halogen Occultation Experiment

The Halogen Occultation Experiment (HALOE) uses solar occultation to measure vertical profiles of O3, HCl, HF, CH4, H2O, NO, NO2, aerosol extinction, and temperature versus pressure with an instantaneous vertical field of view of 1.6 km at the earth limb. Latitudinal coverage is from 80 deg S to 80 deg N over the course of 1 year and includes extensive observations of the Antarctic region during spring. The altitude range of the measurements extends from about 15 km to about 60-130 km, depending on channel. Experiment operations have been essentially flawless, and all performance criteria either meet or exceed specifications. Internal data consistency checks, comparisons with correlative measurements, and qualitative comparisons with 1985 atmospheric trace molecule spectroscopy (ATMOS) results are in good agreement. Examples of pressure versus latitude cross sections and a global orthographic projection for the September 21 to October 15, 1992, period show the utility of CH4, HF, and H2O as tracers, the occurrence of dehydration in the Antarctic lower stratosphere, the presence of the water vapor hygropause in the tropics, evidence of Antarctic air in the tropics, the influence of Hadley tropical upwelling, and the first global distribution of HCl, HF, and NO throughout the stratosphere. Nitric oxide measurements extend through the lower thermosphere.

Russell, James M., III↗
NASA NTRS1993

A model for heterogeneous chemical processes on the surfaces of ice and nitric acid trihydrate particles

The study presents a model that incorporates the physics and physical chemistry of ice surfaces relevant to polar stratospheric clouds. Surface concentrations of H2O, HCl, HOCl, ClONO2, and N2O5 on ice and nitric acid trihydrate (NAT) crystals are computed, and surface reaction rates and reaction probabilities (sticking coefficients) are determined. For gas pressures of about 10 exp -7 torr and temperatures in the range of 180-200 K, HCl completely coats ice and water-rich NAT surfaces, while HOCl, ClOHO2, and N2O5 may cover 0.01-1 percent of these surfaces. The energy parameters are used to calculate surface temperatures such as adsorption and desorption constants, surface coverages, reaction rate coefficients, surface diffusion coefficients, and reaction probabilities for various species and chemical interactions on ice and NAT surfaces. Implications for chemical processing on polar stratospheric clouds are discussed.

Tabazadeh, Azadeh↗
NASA NTRS1993

Elevated initial Sr-87/Sr-86 in ordinary chondrite metal

The metal phase of ordinary chondrites has been found to contain a complex assemblage of non-metal phases, evidently formed when elements such as Si, Cr and P, originally dissolved in the metal, were subsequently oxidized and exsolved. We have investigated the Rb-Sr isotopic system in samples of H-chondrite metal, finding small but nontrivial amounts of Sr, apparently concentrated toward the surface of metal grains, and characterized by pronounced excesses of Sr-87/Sr-86 in chondritic metal can plausibly account for the characteristically elevated initial Sr-87/Sr-86 found in ordinary chondrite phosphates, but it remains unclear when and where the metal experienced the high Rb/Sr environment needed to account for such high Sr-87/Sr-86. We have previously reported Rb-Sr data for separated metal from Dhajala (H3), Forest Vale (H4) and Estacado (H6). Here we report data for two size fractions (80-160 and 280-450 microns) of separated metal from the H4 chondrite Ste. Marguerite. These samples were etched twice (.5N HCl for one hour) before dissolution (6N HCl). Aliquots of the solutions were spiked for Fe, Ca and Rb + Sr. The results for Ste. Marguerite metal are presented; errors are two-sigma and elemental concentrations are stated in terms of total sample weight.

Podosek, F. A.↗
NASA NTRS1994

An overview of the Halogen Occultation Experiment (HALOE) and preliminary results

The Halogen Occultation Experiment (HALOE) experiment has observed vertical profiles and pressure versus latitude cross sections of temperature HCl, HF, CH4, H2O, NO, NO2, O3, and aerosols over the range from 80 deg S to 80 deg N. An in-orbit precision of better than 0.3 ppbv has been demonstrated for HCl, HF, NO, NO2 and less than 0.6 ppmv for the other channels. Comparisons with correlative measurements at this early stage are encouraging. Nitric oxide has been observed over the range from the upper troposphere to 130-km. Latitudinal cross sections of the long-lived tracers CH4 and HF show clear indications of the effect of the general circulation.

Russell, J. M., III↗