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At least 163 records · Page 9

Stratospheric Aerosol Measurements

Stratospheric aerosols affect the atmospheric energy balance by scattering and absorbing solar and terrestrial radiation. They also can alter stratospheric chemical cycles by catalyzing heterogeneous reactions which markedly perturb odd nitrogen, chlorine and ozone levels. Aerosol measurements by satellites began in NASA in 1975 with the Stratospheric Aerosol Measurement (SAM) program, to be followed by the Stratospheric Aerosol and Gas Experiment (SAGE) starting in 1979. Both programs employ the solar occultation, or Earth limb extinction, techniques. Major results of these activities include the discovery of polar stratospheric clouds (PSCs) in both hemispheres in winter, illustrations of the impacts of major (El Chichon 1982 and Pinatubo 1991) eruptions, and detection of a negative global trend in lower stratospheric/upper tropospheric aerosol extinction. This latter result can be considered a triumph of successful worldwide sulfur emission controls. The SAGE record will be continued and improved by SAGE III, currently scheduled for multiple launches beginning in 2000 as part of the Earth Observing System (EOS). The satellite program has been supplemented by in situ measurements aboard the ER-2 (20 km ceiling) since 1974, and from the DC-8 (13 km ceiling) aircraft beginning in 1989. Collection by wire impactors and subsequent electron microscopic and X-ray energy-dispersive analyses, and optical particle spectrometry have been the principle techniques. Major findings are: (1) The stratospheric background aerosol consists of dilute sulfuric acid droplets of around 0.1 micrometer modal diameter at concentration of tens to hundreds of monograms per cubic meter; (2) Soot from aircraft amounts to a fraction of one percent of the background total aerosol; (3) Volcanic eruptions perturb the sulfuric acid, but not the soot, aerosol abundance by several orders of magnitude; (4) PSCs contain nitric acid at temperatures below 195K, supporting chemical hypotheses implicating manmade fluorocarbons as cause of the --'ozone hole'; (5) The current soot loading is too small to be of environmental (radiative and chemical) consequence. However, the fractal nature of soot distinguishes it aerodynamically and radiatively from sulfuric acid droplets such that its stratospheric residence time is longer, mainly because of vertical transport against gravity due to gravito-photophoretic forces. Thus it may accumulate and become of environmental concern in the future.

Pueschel, Rudolf, F.↗

Improved ceramic heat exchange material

Improved corrosion resistant ceramic materials that are suitable for use as regenerative heat exchangers for vehicular gas turbines is reported. Two glass-ceramic materials, C-144 and C-145, have superior durability towards sulfuric acid and sodium sulfate compared to lithium aluminosilicate (LAS) Corning heat exchange material 9455. Material C-144 is a leached LAS material whose major crystalline phase is silica keatite plus mullite, and C-145 is a LAS keatite solid solution (S.S.) material. In comparison to material 9455, material C-144 is two orders of magnitude better in dimensional stability to sulfuric acid at 300 C, and one order of magnitude better in stability to sodium sulfate at 1000 C. Material C-145 is initially two times better in stability to sulfuric acid, and about one order of magnitude better in stability to sodium sulfate. Both C-144 and C-145 have less than 300 ppm delta L/L thermal expansion from ambient to 1000 C, and good dimensional stability of less than approximately 100 ppm delta L/L after exposure to 1000 C for 100 hours. The glass-ceramic fabrication process produced a hexagonal honeycomb matrix having an 85% open frontal area, 50 micrometer wall thickness, and less than 5% porosity.

Mccollister, H. L.↗

Aerosol nucleation in the winter Arctic and Antarctic stratospheres

The formation rate of sulfuric-acid-water aerosol particles is calculated as a function of altitude for the conditions of the winter Arctic and Antarctic stratospheres. The theoretical results indicate that sulfate particle formation can occur in the polar winter stratosphere. Conditions for new particle formation are increasingly favorable as the altitude increases between 20 and 30 km because of the decrease in surface area of preexisting particles and increasing sulfuric-acid vapor supply. The theoretical predictions are consistent with observations of a high-altitude CN layer over Antarctica in the spring. Available vapor-pressure data indicate that ternary particles composed of sulfuric acid, nitric acid, and water are not thermodynamically stable under winter stratospheric conditions.

Hamill, Patrick↗

Physical properties of the stratospheric aerosols

A comparison of the equilibrium vapor pressure over nitric acid solutions with observed water and nitric acid partial pressures in the stratosphere implies that nitric acid cannot be present as an aerosol particle in the lower stratosphere. A similar comparison for sulfuric acid solutions indicates that sulfuric acid aerosol particles are 75% H2SO4 by weight in water, in good agreement with direct observations. The freezing curve of H2SO4 solutions requires that the H2SO4 aerosol particles be solid or supercooled. The equilibrium vapor pressure of H2SO4 in the stratosphere is of the order of 20 picotorr. At stratospheric temperatures, ammonium sulfate is in a ferroelectric phase. As a result, polar molecules may form a surface coating on these aerosols, which may be a fertile ground for further chemical reaction.

Toon, O. B.↗

The atmospheric effects of El Chichon

The eruption of the Mexican volcano El Chichon in late March and early April of 1982 injected an unusually large amount of volcanic material into the stratosphere. This event demonstrates for the first time that a relatively small but sulfur-rich volcanic eruption can produce a dense, widespread stratospheric cloud. Sulfuric acid aerosol is formed by the photochemical reaction of sulfur gases released by a volcano with water vapor in the atmosphere. The aerosol causes a decrease in the mean global temperature because the droplets both absorb solar radiation and scatter it back into space. Attention is given to details concerning the volcanic eruption, the relation of El Chichon to the Mexican and Guatemalan volcanic belts, sources for the sulfur erupted by the volcano, and the mechanisms involved in the formation of sulfuric acid.

Rampino, M. R.↗

Laboratory Simulated Acid-Sulfate Weathering of Basaltic Materials: Implications for Formation of Sulfates at Meridiani Planum and Gusev Crater, Mars

Acid-sulfate weathering of basaltic materials is a candidate formation process for the sulfate-rich outcrops and rocks at the MER rover Opportunity and Spirit landing sites. To determine the style of acid-sulfate weathering on Mars, we weathered basaltic materials (olivine-rich glassy basaltic sand and plagioclase feldspar-rich basaltic tephra) in the laboratory under different oxidative, acid-sulfate conditions and characterized the alteration products. We investigated alteration by (1) sulfuric-acid vapor (acid fog), (2) three-step hydrothermal leaching treatment approximating an open system and (3) single-step hydrothermal batch treatment approximating a "closed system." In acid fog experiments, Al, Fe, and Ca sulfates and amorphous silica formed from plagioclase-rich tephra, and Mg and Ca sulfates and amorphous silica formed from the olivine-rich sands. In three-step leaching experiments, only amorphous Si formed from the plagioclase-rich basaltic tephra, and jarosite, Mg and Ca sulfates and amorphous silica formed from olivine-rich basaltic sand. Amorphous silica formed under single-step experiments for both starting materials. Based upon our experiments, jarosite formation in Meridiani outcrop is potential evidence for an open system acid-sulfate weathering regime. Waters rich in sulfuric acid percolated through basaltic sediment, dissolving basaltic phases (e.g., olivine) and forming jarosite, other sulfates, and iron oxides. Aqueous alteration of outcrops and rocks on the West Spur of the Columbia Hills may have occurred when vapors rich in SO2 from volcanic sources reacted with basaltic materials. Soluble ions from the host rock (e.g., olivine) reacted with S to form Ca-, Mg-, and other sulfates along with iron oxides and oxyhydroxides.

Golden, D. C.↗

Advanced double layer capacitors

There is a need for large amounts of power to be delivered rapidly in a number of airborne and space systems. Conventional, portable power sources, such as batteries, are not suited to delivering high peak power pulses. The charge stored at the electrode-electrolyte double layer is, however, much more assessible on a short time scale. Devices exploiting this concept were fabricated using carbon and metal oxides (Pinnacle Research) as the electrodes and sulfuric acid as the electrolyte. The approach reported, replaces the liquid sulfuric acid electrolyte with a solid ionomer electrolyte. The challenge is to form a solid electrode-solid ionomer electrolyte composite which has a high capacitance per geometric area. The approach to maximize contact between the electrode particles and the ionomer was to impregnate the electrode particles using a liquid ionomer solution and to bond the solvent-free structure to a solid ionomer membrane. Ruthenium dioxide is the electrode material used. Three strategies are being pursued to provide for a high area electrode-ionomer contact: mixing of the RuOx with a small volume of ionomer solution followed by filtration to remove the solvent, and impregnation of the ionomer into an already formed RuOx electrode. RuOx powder and electrodes were examined by non-electrochemical techniques. X-ray diffraction has shown that the material is almost pure RuO2. The electrode structure depends on the processing technique used to introduce the Nafion. Impregnated electrodes have Nafion concentrated near the surface. Electrodes prepared by the evaporation method show large aggregates of crystals surrounded by Nafion.

Sarangapani, S.↗

The photochemistry of a remote marine stratiform cloud

The coupled gas- and aqueous-phase photochemistry of a stratiform cloud in a remote region of the marine atmosphere is investigated with a time-dependent box model. Both scavenging of ambient acidic aerosols and gases as well as aqueous-phase chemical reactions within droplets are found to be important sources of acidity to cloud water and can lead to pH levels in cloud water in the remote marine atmosphere well below 5.6. The major sources of acidity via aqueous-phase chemical reactions are the generation of sulfuric acid from dissolved SO2 and the generation of formic acid from dissolved formaldehyde. In both cases, aqueous-phase free radicals can play a significant role either directly by oxidizing dissolved SO2 and HCHO or indirectly by producing the aqueous-phase oxidant H2O2. The rate of SO2 conversion to sulfuric acid is sensitive to a variety of parameters including the accommodation or sticking coefficient for SO2, H2O2, HO2, and OH, the liquid water content, and the ambient levels of SO2, HNO3, and other acidic or basic gases. Because high levels of SO2 tend to deplete cloud water of H2O3, the possibility exists that the pH of precipitation in polluted regions will respond nonlinearly to reduced SO2 emissions.

Chameides, W. L.↗

Ion-induced nucleation in a binary mixture

Recent ion-induced nucleation studies in a binary mixture of H2O and H2SO4 vapors indicate that conventional classical nucleation theories cannot account for the experimentally observed ion-H2O-H2SO4 microcluster spectra. An empirical-analytical, semi-molecular theory of nucleation of a binary mixture of vapors on ions has been developed. This theory includes molecular approach to ion-induced changes in dielectric properties in the immediate neighborhood of an ion core as well as the size dependence of the surface tension of the microcluster. In addition to gaseous sulfuric acid and water molecules, the effect of ion-hydrates and sulfuric acid hydrates has also been considered. This theory is further simplified by using an empirical correction factor for the electrostatic term. This correction factor has been obtained by comparing the simplified model with the molecular dynamics calculations for selected ion hydrate formation. These two theoretical models are then compared with the classical theory for a variety of experimental conditions.

Smith, A. C.↗

Study and interpretation of the millimeter-wave spectrum of Venus

The effects of the Venus atmospheric constituents on its millimeter wavelength emission are investigated. Specifically, this research describes the methodology and the results of laboratory measurements which are used to calculate the opacity of some of the major absorbers in the Venus atmosphere. The pressure broadened absorption of gaseous SO2/CO2 and gaseous H2SO4/CO2 has been measured at millimeter wavelengths. We have also developed new formalisms for computing the absorptivities of these gases based on our laboratory work. The complex dielectric constant of liquid sulfuric acid has been measured and the expected opacity from the liquid sulfuric acid cloud layer found in the atmosphere of Venus has been evaluated. The partial pressure of gaseous H2SO4 has been measured which results in a more accurate estimate of the dissociation factor of H2SO4. A radiative transfer model has been developed in order to understand how each atmospheric constituent affects the millimeter wave emissions from Venus. Our results from the radiative transfer model are compared with recent observations of the micro-wave and millimeter wave emissions from Venus. Our main conclusion from this work is that gaseous H2SO4 is the most likely cause of the variation in the observed emission from Venus at 112 GHz.

Fahd, Antoine K.↗

Formation and Stability of Radiation Products in Europa's Icy Shell

Spectra of Europa reveal a surface dominated by water-ice along with hydrated materials and minor amounts of SO2, CO2, and H2O2. Jovian magnetospheric ions (protons, sulfur, and oxygen) and electrons produce significant chemical modifications of the surface on time scales of a few years at micrometer depths. Our laboratory studies examine the formation and stability of radiation products in H2O-rich ices relevant to Europa. Infrared (IR) spectra of ices before and after irradiation reveal the radiation destruction of molecules and the formation of products at 86 - 132 K. In addition, spectra of ices during warming track thermal evolution due to chemical changes and sublimation processes. IR-identified radiation products in 86 - 132 K irradiated H2O + SO2 ices are the bisulfate ion, HSO4(-), sulfate ion, SO4(2-) and the hydronium ion, H3O(+). Warming results in the formation of a residual spectrum similar to liquid sulfuric acid, H2SO4, for H2O:SO2 ratios of 30:1, whereas hydrated sulfuric acid, H2SO4 4 H2O, forms for ratios of 30:1. Radiation products identified for irradiated H2O + H2S ices at 86 K are H2S2 and SO2. When irradiated at 110 and 132 K, ices with H2O:H2S ratios if either 3:1 or 30:1 show the formation of H2SO4 4 H2O on warming to 175 K. We have also examined the radiation stability of H2SO4. Addition of CO2 to H2O + SO2 ices results in the formation of CO3 at 2046 cm (sup -1) (4.89 m). This is the strongest band from a carbon-containing product in the mid-IR spectral region, and it is also seen when either pure CO2 or H2O + CO2 ice is irradiated. Experiments with CH4 added to H2O + SO2 + CO2 ices addressed the question of methane's use as a marker of methanogens in an irradiated ice environment. New results on the near-IR spectrum of pure H2O2 will be included in this presentation. Interpretations of near-IR water bands, with H2O2 present, will be discussed. Irradiations of H2O2 and H2O + H2O2 mixtures, to examine the possibility of O2 and O3 formation, are currently under investigation and new results will be discussed.

Moore, M. H.↗

Friction and Wear of Iron in Corrosive Media

Friction and wear experiments were conducted with elemental iron exposed to various corrosive media including two acids, base, and a salt. Studies involved various concentrations of nitric and sulfuric acids, sodium hydroxide, and sodium chloride. Load and reciprocating sliding speed were kept constant. With the base NaOH an increase in normality beyond 0.01 N resulted in a decrease in both friction and wear. X-ray photoelectron spectroscopy (XPS) analysis of the surface showed a decreasing concentration of ferric oxide (Fe2O3) on the iron surface with increasing NaOH concentration. With nitric acid (HNO3) friction decreased in solutions to 0.05 N, beyond which no further change in friction was observed. The concentration of Fe2O3 on the surface continued to increase with increasing normality. XPS analysis revealed the presence of sulfates in addition of Fe2O3 on surfaces exposed to sulfuric acid and iron chlorides but no sodium on surfaces exposed to NaCl.

Rengstorff, G. W. P.↗

Intumescent composition, foamed product prepared therewith, and process for making same

An intumescent composition and the foamed product prepared by heating are discussed wherein the composition comprises the reaction product of para-benzoquinone dioxime and a concentrated mineral acid such as sulfuric acid, phosphoric acid, and polyphosphoric acid. The composition is useful as an intumescent agent either by itself or when combined with other materials. A fire-resistant and heat-insulating composition is provided by heating the intumescent composition above its intumescent temperature.

Riccitiello, S. R.↗

Intumescent composition, foamed product prepared therewith and process for making same

An intumescent composition and the foamed product prepared by heating the composition are provided. The composition comprises the reaction product of para-benzoquinone dioxime and a concentrated mineral acid such as sulfuric acid, phosphoric acid, and polyphosphoric acid. The composition is useful as an intumescent agent either by itself or when combined with other materials. A fire-resistant and heat-insulating composition is provided by heating the intumescent composition above its intumescent temperature.

Riccitiello, S. R.↗

Ambient cure polyimide foams

Flame and temperature resistant polyimide foams are prepared by the reaction of an aromatic dianhydride, (pyromellitic dianhydride) with an aromatic polyisocyanate, (polymethylene polyphenylisocyanate), in the presence of an inorganic acid and furfuryl alcohol. Usable acids include dilute sulfuric acid, dilute nitric acid, hydrochloric acid, polyphosphoric acid, and phosphoric acid, with the latter being preferred. The dianhydride and the isocyanate in about equimolar proportions constitute about 50% of the reaction mixture, the rest being made up with the acid and the alcohol in a ratio of about 1:10. An exothermic reaction between the acid and the alcohol provides the heat necessary for the other components to polymerize without recourse to external heat sources. The mixture can be sprayed on any surface to form polymeric foam in locations where the application of heat is not practical or possible, for instance, between walls or on mine tunnel surfaces.

Sawko, P. M.↗

Laboratory chemistry and stratospheric clouds

Results are presented from laboratory experiments on the chemistry of ice particles to study the role of HCl and ClONO2 from CFCs in stratospheric ozone depletion over Antarctica. It is found that gaseous HCl is scavenged with high efficiency by the ice and the gas phase chlorine nitrate may react with the HCL-containing ice to produce Cl2. Also, consideration is given ot the behavior of solid nitric acid trihydrate and sulfuric acid aerosols.

Molina, Mario J.↗