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At least 757 records · Page 42
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Condensational growth and trace species scavenging in stratospheric sulfuric acid/water aerosol droplets

Stratospheric aerosols play a significant role in the environment. The composition of aerosols is believed to be a liquid solution of sulfuric acid and water with numerous trace species. Of these trace species, ozone in particular was recognized as being very important in its role of shielding the environment from harmful ultraviolet radiation. Also among the trace species are HCl and ClONO2, the so called chlorine reservoir species and various oxides of nitrogen. The quantity of stratospheric aerosol and its particle size distribution determines, to a large degree, the chemistry present in the stratosphere. Aerosols experience 3 types of growth: nucleation, condensation, and coagulation. The application of condensation investigations to the specific problem of stratospheric aerosols is discussed.

Tompson, Robert V., Jr.↗
NASA NTRS1990

Far infrared balloon-based limb emission measurements of HO(sub x) gases in the middle atmosphere

The aim of the measurements is to obtain vertical mixing of profiles of hydrogen and halogen trace gases and to study the related processes of diurnal change, OH/HO2 ratio, and HO sub x total budget involved in stratospheric ozone. The species to be measured in the first planned 1990 flight of this new series include OH, H2O2, HO2, HOCl, HBr, HCl, HF, H2O, HDO, O3, and isotopic O3. Recent analyses have been completed for the retrieval of the OH concentration profile and the first measurement of the HBr column concentration.

Russell, James M., III↗
NASA NTRS1990

Tunable far infrared studies of molecular parameters in support of stratospheric measurements

The purpose of this research is to make precise, fully line-resolved measurements of molecular parameters that are necessary for the analysis of spectra obtained in far infrared field measurement programs. These measurements make it possible to accurately analyze the data from field measurements to obtain atmospheric concentration profiles of key trace gases involved in the ozone chemistry. The research objectives include: measurements of pressure broadening of molecular lines of OH, O2, O3, HCl, and H2O, their temperature dependence, and, when possible, the pressure-induced frequency shifts of the lines; measurements of line positions of radical species, such as HO2.

Chance, K. V.↗
NASA NTRS1990

Natural chlorine and fluorine in the atmosphere, water and precipitation

The geochemical cycles of chlorine and fluorine are surveyed and summarized as framework for the understanding of the global natural abundances of these species in the atmosphere, water, and precipitation. In the cycles the fluxes into and out of the atmosphere can be balanced within the limits of our knowledge of the natural sources and sinks. Sea salt from the ocean surfaces represent the predominant portion of the source of chlorine. It is also an important source of atmospheric fluorine, but volcanoes are likely to be more important fluorine sources. Dry deposition of sea salt returns about 85 percent of the salt released there. Precipitation removes the remainder. Most of the sea salt materials are considered to be cyclic, moving through sea spray over the oceans and either directly back to the oceans or deposited dry and in precipitation on land, whence it runs off into rivers and streams and returns to the oceans. Most of the natural chlorine in the atmosphere is in the form of particulate chloride ion with lesser amounts as gaseous inorganic chloride and methyl chloride vapor. Fluorine is emitted from volcanoes primarily as HF. It is possible that HF may be released directly form the ocean surface but this has not been confirmed by observation. HCl and most likely HF gases are released into the atmosphere by sea salt aerosols. The mechanism for the release is likely to be the provision of protons from the so-called excess sulfate and HNO3. Sea salt aerosol contains fluorine as F(-), MgF(+), CaF(+), and NaF. The concentrations of the various species of chlorine and fluorine that characterize primarily natural, unpolluted atmospheres are summarized in tables and are discussed in relation to their fluxes through the geochemical cycle.

Friend, James P.↗
NASA NTRS1989

Trends in stratospheric minor constituents

Photochemical models predict that increasing source gas concentrations are also expected to lead to changes in the concentrations of both catalytically active radical species (such as NO2, ClO, and OH) and inactive reservoir species (such as HNO3, HCl, and H2O). For simplicity, we will refer to all these as trace species. Those species that are expected to have increasing concentration levels are investigated. Additionally, the trace species concentration levels are monitored for unexpected changes on the basis of the measure increase in source gases. Carrying out these investigations is difficult due to the limited data base of measurements of stratospheric trace species. In situ measurements are made only infrequently, and there are few satelliteborne measurements, most over a time space insufficient for trend determination. Instead, ground-based measurements of column content must be used for many species, and interpretation is complicated by contributions from the troposphere or mesosphere or both. In this chapter, we examine existing measurements as published or tabulated.

Stolarski, R. S.↗
NASA NTRS1991

Thermodynamic models of the chemistry of lunar volcanic gases

Thermodynamic models and mass-balance arguments are used to constrain the chemistry of lunar volcanic gases. The results predict that lunar gases were dominated by reduced C and S gases such as CO, COS, CS2, S2. The more oxidized gases CO2 and SO2 were also important, but only in limited temperature ranges. Gases such as Cl2, CCl4, and CF4 were more abundant than HF and HCl, which were the two major H compounds in the lunar gases. Chlorides and fluorides were important species for transporting many volatile and ore-forming metals, and the implications for fractionating and concentrating metals into lunar ore-deposits merit further study.

Fegley, Bruce, Jr.↗
NASA NTRS1992

The molecular core in G34.3 + 0.2 - Millimeter interferometric observations of HCO(+), H(C-13)N, H(C-15)N, and SO

This study presents high-resolution observations of the molecular core in the star-forming region G34.3 + 0.2. Maps at 6-arcsec resolution of emission and absorption of the J = 1 - 0 transitions of HCO(+), H (C-13)N, H(C-15)N, and of the 2(2) - 1(1) transition of SO were obtained in addition to a map of the 3.4-mm continuum emission from the compact H II component. The HCL(+) emission toward G34.3 + 0.2 traces a warm molecular core about 0.9 pc in size. Emission from H (C-13)N is detected over about 0.3 pc. The cometary H II region lies near the edge of the molecular core. The blueshift of the radio recombination lines with respect to the molecular emission suggests that gas from the H II region is accelerated in a champagne flow caused by a steep gradient in the ambient gas density.

Carral, Patricia↗
NASA NTRS1992

Photochemical partitioning of the reactive nitrogen and chlorine reservoirs in the high-latitude stratosphere

The correlated set of measurements in the lower stratosphere from polar missions of the NASA ER-2 is used to derive partitioning of the major components of the reactive nitrogen and inorganic chlorine reservoirs. The results provide a consistent method for comparing distributions, and hence the controlling processes, between different areas of the near-polar regions. Clear evidence of the effects of heterogeneous processes in the atmosphere is found. Values for NO2, ClONO2, N2O5, and Cl2O2 are derived in a simplified steady-state model based on in situ NO, ClO, O3, temperature, and pressure measurements, laboratory-measured reaction rates; and modeled photodissociation rates. Values for the reservoir totals are independently derived from measurements of N2O, organic chlorine, and total reactive nitrogen. The relative abundances of the measured and derived species within the reservoirs are calculated, and the longer-lived species HCl and HNO3 are estimated as the residuals of their respective reservoirs.

Kawa, S. R.↗
NASA NTRS1992

Composition measurements of the 1989 Arctic winter stratosphere by airborne infrared solar absorption spectroscopy

The paper reports simultaneous measurements of the stratospheric burdens of H2O, HDO, OCS, CO2, O3, N2O, CO, CH4, CF2Cl2, CFCl3, CHF2Cl, C2H6, HCN, NO, NO2, HNO3, ClNO3, HOCl, HCl, and HF made by the JPL MkIV interferometer on board the NASA DC-8 aircraft during January and early February 1989 as part of the Airborne Arctic Stratosphere Experiment. Data were obtained on 11 flights at altitudes of up to 12 km over a geographic region covering the NE Atlantic Ocean, Iceland, and Greenland. Analyses of the chemically active gases reveal highly perturbed conditions within the vortex. The ClNO3 abundance was chemically enhanced near the edge of the vortex but was then depleted inside. NO2 was severely depleted inside the vortex. In contrast to Antarctica, H2O and HNO3 were both more abundant inside the vortex than outside. It is suggested that although the Arctic vortex did not get cold enough to produce any dehydration, or as vertically extensive denitrification as occurred in Antarctica, nevertheless, enough heterogeneous chemistry occurred to convert over 90 percent of the inorganic chlorine to active forms in the 14- to 27-km altitude range by early February 1989.

Toon, G. C.↗
NASA NTRS1992

Episodic total ozone minima and associated effects on heterogeneous chemistry and lower stratospheric transport

Three-dimensional model simulations are used to describe the January 31, 1989 ozone minihole over Stavanger, Norway. This minihole is typical of many transient events in the lower stratosphere that arise because of cyclonic-scale disturbances in the troposphere. Although the ozone reduction is a short-lived reversible dynamical event, through heterogeneous chemical processes there can be a significant transfer of chlorine from reservoir molecules to active radicals. This chemically perturbed air is defined as processed air, and it is found that a single event can produce enough processed air to reduce the HCl in the entire polar vortex. Chemical processing on clouds associated with transient events is shown to be a major source of processed air in the polar vortex in December before background temperatures are cold enough for more uniform heterogeneous conversion.

Rood, Richard B.↗
NASA NTRS1992

Schroedinger's radial equation - Solution by extrapolation

A high-accuracy numerical method for the solution of a 1D Schroedinger equation that is suitable for a diatomic molecule, obtained by combining a finite-difference method with iterative extrapolation to the limit, is presently shown to have several advantages over more conventional methods. Initial guesses for the term values are obviated, and implementation of the algorithm is straightforward. The method is both less sensitive to round-off error, and faster than conventional methods for equivalent accuracy. These advantages are illustrated through the solution of Schroedinger's equation for a Morse potential function suited for HCl and a numerically derived Rydberg-Klein-Rees potential function for the X 1Sigma(+) state of CO.

Goorvitch, D.↗
NASA NTRS1992

The 1985 chlorine and fluorine inventories in the stratosphere based on ATMOS observations at 30 deg North latitude

Results are presented of an investigation of the Cl and F inventories derived from the concentrations of eleven Cl- and F-bearing organic and inorganic species throughout the atmosphere, based on observations with the Atmospheric Trace Molecule Spectroscopy instrument aboard the Space Shuttle during the Spacelab 3 mission of April 29 to May 6, 1985. It was found that, in April-May 1985, near 30 deg N, the mean total stratospheric concentrations of Cl and F were 2.58 +/-0.10 ppbv and 1.15 +/-0.12 ppbv, respectively. Partitioning among the source, sink, and reservoir species was consistent with the conservation of the F and Cl budgets throughout the stratosphere. It is shown that the budgets of Cl and F above about 45 km altitude can be determined accurately by measuring only HCl, HF, and CF4 and provide a straightforward timely reference point for future inventories and trends evaluations.

Zander, R.↗
NASA NTRS1992

Chemical isolation of quartz for measurement of in-situ-produced cosmogenic nuclides

An isolation method relying totally on chemical steps was developed to separate large quantities (10-200 g) of clean mono-minerallic quartz samples from a variety of terrestrial rocks and soils for the purpose of measuring Be-10 (t1/2 = 1.5 Myr) and Al-26 (t1/2 = 0.705 Myr) produced by cosmic rays in situ in the quartz phase. The procedure consists of grinding the sample, heating it in HCl, and treating it with a series of leaches using a dilute HF/HNO3 mixture in a heated ultrasonic tank. The purified quartz was also used for the measurements of in situ cosmic-ray-produced Ne-21 and C-14 (t1/2 = 5730 yr). The method is applicable to any problem requiring purified quartz on a large scale.

Kohl, C. P.↗
NASA NTRS1991

Predicted rocket and shuttle effects on stratospheric ozone

The major chemical effluents of either solid- or liquid-fueled rockets that can potentially perturb stratospheric ozone include chlorine compounds (HCl), nitrogen compounds (NO(x)), and hydrogen compounds (H2 and H2O). Radicals (Cl, ClO, H, OH, HO2, NO, and NO2) formed directly or indirectly from rocket exhaust can cause the catalytic destruction of ozone. Other exhaust compounds that could presumably lead to ozone destruction either by direct reaction with ozone or by providing a surface for heterogeneous processes include the particulates Al2O3, ice, and soot. These topics are discussed in terms of the possible effects of rocket exhausts on stratospheric ozone.

Harwood, Robert S.↗
NASA NTRS1992

Stratospheric aircraft exhaust plume and wake chemistry studies

This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3.

Miake-Lye, R. C.↗
NASA NTRS1992

Implications for volcanogenic volatile release on the weathering of Mars

Volcanism on Mars has been widespread in both space and time. Notwithstanding important specific differences between the mantles of Earth and Mars, the similarities are such that the suite of gases emitted from martian volcanic activity surely includes gases such as H2O, CO2, S-containing gases (H2S, SO3, or SO2), and Cl-containing gases (e.g. Cl or HCl). Both H2O and CO2 are present in the atmosphere of Mars; both are also present as surface condensates. Spectroscopic observations of the martian atmosphere clearly show that the S- and Cl-containing gases are severely depleted. Likewise, there is no evidence of surface condensates of compounds of these elements. Within the soil, there is direct evidence of incorporation of H2O and some compounds of sulfur and chlorine. None of the resultant weathering products have been directly identified, but both clays and salts have been indirectly implicated. Other aspects of the implications for volcanogenic volatile release on the weathering of Mars are discussed.

Clark, Benton C.↗
NASA NTRS1992

Chemical modeling constraints on Martian surface mineralogies formed in an early, warm, wet climate, and speculations on the occurrence of phosphate minerals in the Martian regolith

This is one in a series of reports summarizing our chemical modeling studies of water-rock-gas interactions at the martian surface through time. The purpose of these studies is to place constraints on possible mineralogies formed at the martian surface and to model the geochemical implications of martian surficial processes proposed by previous researchers. Plumlee and Ridley summarize geochemical processes that may have occurred as a result of inferred volcano- and impact-driven hydrothermal activity on Mars. DeBraal et al. model the geochemical aspects of water-rock interactions and water evaporation near 0 C, as a prelude to future calculations that will model sub-0 C brine-rock-clathrate interactions under the current martian climate. In this report, we discuss reaction path calculations that model chemical processes that may have occurred at the martian surface in a postulated early, warm, wet climate. We assume a temperature of 25 C in all our calculations. Processes we model here include (1) the reaction of rainwater under various ambient CO2 and O2 pressures with basaltic rocks at the martian surface, (2) the formation of acid rain by volcanic gases such as HCl and SO2, (3) the reactions of acid rain with basaltic surficial materials, and (4) evaporation of waters resulting from rainwater-basalt interactions.

Plumlee, Geoffrey S.↗
NASA NTRS1992

Stratospheric minor constituent distributions from far-infrared thermal emission spectra

We retrieve mixing ratio profiles of O3, H2(O-16), H2(O-17), H2(O-18), HF, and HCl from far-infrared thermal emission observations of the limb in the 80-220 cm/sec spectral region. The observations were made with a balloon-borne Fourier transform spectrometer as a part of the 1983 Balloon Intercomparison Campaign (BIC-2). A subset of the data was analyzed previously using the method in the work of Traub et al. (1982, 1991); in the present paper we use an alternative method of calibration and analysis, given by Abbas et al. (1985). The retrieved constituent profiles are compared with the measurements made with other instruments on the BIC-2 flights. The results for the concentrations of H2(O-17) and H2(O-18) obtained in this study indicate no isotopic enhancement or depletion with a standard deviation of about 20 percent.

Abbas, Mian M.↗