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At least 217 records · Page 12

Isotopic anomalies of Ne, Xe, and C in meteorites. I - Separation of carriers by density and chemical resistance

The carriers of presolar noble gases were studied by isotopically analyzing 19 separates from the Murray and Murchison C2 chondrites for Ne, Xe, C, and N. It is found that the carriers of Ne-E(H) and Xe-S are resistant to HCl, HF, boiling HClO4, and CrO3-H2SO4, and thus must be either diamond or some resistant carbide or oxide. The carrier of Ne-E(L) may be some form of amorphous carbon with delta C13 of about +340 percent. A new carbon component, C theta, found as 0.2-2-micron inclusions in Murchison spinel, is amorphous and contains little or no noble gas. A new heavy nitrogen component is found which has an abundance of about 1 ppm in the bulk meteorite, combusts at 450-500 C, and may be associated wtih isotopically normal carbon or with C-alpha.

Ming, Tang↗

Ozone destruction through heterogeneous chemistry following the eruption of El Chichon

The results of ozone observations at northern midlatitudes in late 1982 through 1983, following the eruption of El Chichon are discussed, together with the observations of other trace gases which may be linked to possible variations in ozone chemistry. These results are related to the in situ aerosol observations following the El Chicon eruption, with particular attention given to data relevant to heterogeneous reactions, such as the aerosol surface area and weight percent H2SO4. It is shown that, at midlatitudes, the observed volcanic-particle surface area reached a maximum of about 50 sq microns/cu m (above a typical background value of about 0.75) at an altitude of 18-20 km in early 1983; this enhancement of surface area is about the same as that encountered in stratospheric clouds in the Antarctic, suggesting a possible basis for ozone depletion through heterogeneous chemistry. The fraction of ozone reduction that may have occurred as a result of heterogeneous chemicl effects is estimated.

Hofmann, David J.↗

Wet chemical techniques for passivation of YBa2Cu3O7(7-x)

Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, resulting in the formation of native compounds with little or no reactivity to water. Promising native compounds include CuI, BaSO4, CuS, Cu2S, and the oxalates, all of which are either insoluble or have very low solubility in water. Treatment with dilute HI results in the formation of a native iodide film which is 80-90 percent CuI with small amounts of YI3 and BaI2. Treatment with dilute H2SO4 results in the formation of a film which is 95 percent BaSO4 and 5 percent Y2(SO4)3. Cu2S is formed on the surface with a dilute Na2S solution. An oxalate film with equal amounts of Y2(C2O4)3 and BaC2O4 results from treatment with dilute oxalic acid. X-ray photoelectron spectra show no significant changes when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide film shows evidence of Cu(OH)2 formation.

Vasquez, R. P.↗

Wet chemical passivation of YBa2Cu3O(7-x)

Wet chemical techniques are described for treatment of YBa2Cu3O(7-x) surfaces, which result in the formation of native compounds known to have little or no reactivity to water. Suitable native compounds include CuI, BaSO4, CuS, Cu2S, YF3, and the oxalates. Formation of surface layers in which these nonreactive native compounds are major constituents is verified with X-ray photoelectron spectroscopy (XPS) measurements on YBa2Cu3O(7-x) films treated with dilute solutions of HI, H2SO4, Na2S, HF, or H2C2O4. No significant changes are observed in the XPS spectra when the sulfide, sulfate, or oxalate films are dipped in water, while the iodide and fluoride films show evidence of reaction with water. X-ray diffraction measurements show that the superconducting phase is absent in the sulfide film, but is unaffected by the oxalate and sulfate treatments.

Vasquez, R. P.↗

Space environmental effects on spacecraft thermal control coatings

A large portion of the space based applications in the near future are for low Earth orbit (LEO) including the Space Station Freedom (SSF). The lifetime needs for materials on the SSF is 30 years. Materials must be selected which can withstand the deleterious effects of LEO. Environmental effects in the LEO include atomic oxygen, UV, ionizing radiation, and hypervelocity impact. These effects can adversely affect the surface properties of materials. This is particularly critical in the case of thermal control materials where the efficiency of the thermal control is dependent on the stability of the surface properties. The current baseline thermal coating for the SSF radiators is Ag Teflon. The surface property requirements for the coatings are a solar absorptance of 0.2 and an infrared emittance of 0.8. The effects of atomic oxygen and UV radiation on the baseline coating and several other candidate thermal control materials were studied. The thermal control radiator materials included Ag and Al backed Teflon, H2SO4 anodized Al, sputter deposited SiO2 on Al, and Ag and Al backed polychloro trifluoroethylene. The simulation of several of the LEO environment constituents provided a data base to aid in the selection of the radiator thermal control material to meet the life requirements of the SSF. The effects are illustrated of the environment on thermal control coatings and the importance of this factor in the selection process for long life spacecraft materials.

Bartosik, L. G.↗

Composition and spectral characteristics of ambient aerosol at Mauna Loa Observatory

The spectral and the chemical characteristics of ambient aerosol at Mauna Loa Observatory (Hawaii) were determined in aerosol particles continuously sampled during an 8-day period in August 1986. During this period, the chemical species in the ambient aerosol varied considerably. During the major fraction of the sampling period, the aerosol was acidic due to predominance of (NH4)3H(SO4)2, NH4HSO4, or H2SO4. Aerosol samples showed much higher absorbance at 9.1 microns than at 10.6 microns. Moreover, changes in chemical composition from the neutral (NH4)2SO4 aerosol to more acidic sulphate forms were accompanied by substantial changes in the samples' absorbance at 9.1 microns (with lesser changes in the 10.6-micron absorptions).

Johnson, Stanley A.↗

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.↗

Spectroscopic observations of bright and dark emission features on the night side of Venus

Near-infrared spectra of a bright and a dark thermal emission feature on the night side of Venus have been obtained from 2.2 to 2.5 microns at a spectral resolution of 1200 to 1500. Both bright and dark features show numerous weak absorption bands produced by CO2, CO, water vapor, and other gases. The bright feature emits more radiation than the dark feature throughout this spectral region, but the largest contrasts occur between 2.21 s 2.32 microns, where H2SO4 clouds and a weak CO2 band provide the only known sources of extinction. The contrast decreases by 55 to 65 percent at wavelengths longer than 2.34 microns, where CO, clouds, and water vapor also absorb and scatter upwelling radiation. This contrast reduction may provide direct spectroscopic evidence for horizontal variations in the water vapor concentrations in the Venus atmosphere at levels below the cloud tops.

Bell, J. F., III↗

Middle infrared thermal maps of Venus at the time of the Galileo encounter

Images of the disk of Venus, taken at wavelengths between 8 and 22 micrometers, were obtained a few days after the Galileo spacecraft's closest approach on February 8, 1990; these images show variations in the thickness of the main H2SO4 cloud deck and the overlying temperature structure. Several features are qualitatively similar to those of earlier observations, such as a hot region at the south pole, surrounded by a cold 'collar', and brightening toward the lower latitudes, where low-contrast banding appears. The collar does have a northern counterpart that is warmer, however. Equatorial limb darkening is quantitatively similar to that of previous observations; fairly constant at wavelengths up to 20 micrometers, where limb darkening increases substantially. In contrast to what was found in previous observations, polar and equatorial limb darkening are nearly the same at most wavelengths. A longitudinal variation is observable that is consistent with a wavenumber-2 behavior and a brightness maximum near local midnight.

Orton, Glenn S.↗

Homogeneous freezing nucleation of stratospheric solution droplets

The classical theory of homogeneous nucleation was used to calculate the freezing rate of sulfuric acid solution aerosols under stratospheric conditions. The freezing of stratospheric aerosols would be important for the nucleation of nitric acid trihydrate particles in the Arctic and Antarctic stratospheres. In addition, the rate of heterogeneous chemical reactions on stratospheric aerosols may be very sensitive to their state. The calculations indicate that homogeneous freezing nucleation of pure water ice in the stratospheric solution droplets would occur at temperatures below about 192 K. However, the physical properties of H2SO4 solution at such low temperatures are not well known, and it is possible that sulfuric acid aerosols will freeze out at temperatures ranging from about 180 to 195 K. It is also shown that the temperature at which the aerosols freeze is nearly independent of their size.

Jensen, Eric J.↗

Radio observations of the planets - The importance of laboratory measurements

Laboratory data on the line broadening parameters of H2S gas under Uranian/Neptunian conditions, on the far wings of the H2S and NH3 line profiles, and on the dielectric properties of CH4-, NH3-, H2S-, and NH4SH-ice are needed to constrain elemental abundances and understand the dynamics and cloud physics in the atmospheres of the giant planets. Measurements of the absorption coefficient of gaseous H2SO4 at millimeter wavelengths are needed in order to obtain a better understanding of Venus' atmosphere. To determine wind velocity fields in Venus' and Mars' atmospheres, accurate measurements of the center frequencies of the CO lines are necessary. The absorption and scattering properties of lunar soils and/or terrestrial rock powders at frequencies from approximately 1 to 200 GHz, determined in laboratory experiments, would provide a valuable addition to existing data at 450 MHz, 35 GHz, and far infrared frequencies. These data would be used to analyze the microwave spectra of planetary surfaces. Such studies may be helpful in distinguishing the effects of radiative transfer from those of nonlinear heat conduction and internal heat sources.

De Pater, Imke↗

Modified HNO3 seasonality in volcanic layers of a polar ice core - Snow-pack effect or photochemical perturbation?

Changes in atmospheric HNO3 chemistry following the Laki (1783), Tambora (1815), and Katmai (1912) volcanic eruptions are presently investigated in view of a central Greenland ice core's chemical composition. Attention is given to the concentration of several cations and anions, using ion chromatography. Following the eruptions, the ratio of winter to summer depositions of NO3(-) was significantly higher than during nonvolcanic periods. While this may be due to ice pack effects, it is proposed that large concentrations of the stratospheric H2SO4 particles ejected by the volcanoes favored HNO3 removal during Arctic winter.

Laj, Paolo↗

Projectile-target mixing in melted ejecta formed during a hypervelocity impact cratering event

Tektites contain little to no projectile contamination while, in contrast, some distal ejecta deposits can be relatively projectile-rich (e.g. the Cretaceous-Tertiary (K-T) boundary clay). This compositional difference motivated an experimental study of hypervelocity target-projectile mixing processes. We hope to scale up the results from these experiments and apply them to terrestrial impact structures like the Chicxulub Crater, Yucutan, Mexico, the leading contender as the site for the impact that caused the mass extinction that marks the K-T boundary. Shock decomposition of the approximately 500m thickness of anhydrite, or greater thickness of limestone, in the target rocks at Chicxulub may have been a critical mechanism for either global cooling via SO3, and subsequently H2SO4, formation, or possibly, global warming via increased CO2 formation. Understanding target-projectile mixing processes during hypervelocity impact may permit more accurate estimates of the amount of potentially toxic, target-derived material reaching stratospheric heights.

Evans, Noreen Joyce↗

The fractionation of noble gases in diamonds of CV3 Efremovka chondrite

It was shown that in diamonds of Efremovka CV3 the noble gases with normal isotopic compositions are fractionated in different degree while the correlation of isotopic anomalous components is nearly constant. Some data for noble gases in DE-4 sample of Efremovka chondrite are considered. In contrast to DE-2 sample the DE-4 was treated except conc. HClO4, 220 C in addition with mixture of conc. H2SO4+H3PO4 (1:1), 220 C, twice. Noble gases analysis were performed in Germany at Max Plank Institute fur Chemie. Noble gases were released by oxidation of samples at stepped heating from 420 C to 810 C and by pyrolysis at 580, 590, and 680 C.

Fisenko, A. V.↗

Laboratory studies of chemical and photochemical processes relevant to stratospheric ozone

The purpose of this project is to reduce the uncertainty in several key gas-phase kinetic processes which impact our understanding of stratospheric ozone. The main emphasis of this work is on measuring rate coefficients and product channels for reactions of HO(sub x) and NO(sub x) species in the temperature range 200 K to 240 K relevant to the lower stratosphere. Other areas of study have included infrared spectroscopic studies of the HO2 radical, measurements of OH radical reactions with alternative fluorocarbons, and determination of the vapor pressures of nitric acid hydrates under stratospheric conditions. The results of these studies will improve models of stratospheric ozone chemistry and predictions of perturbations due to human influences. In this annual report, we focus on our recent accomplishments in the quantitative spectroscopy of the HO2 radical. This report details the measurements of the broadening coefficients for the v(sub 2) vibrational band. Further measurements of the vapor pressures of nitric acid hydrates relevant to the polar stratospheric cloud formation indicate the importance of metastable crystalline phases of H2SO4, HNO3, and H2O. Large particles produced from these metastable phases may provide a removal mechanism for HNO3 in the polar stratosphere.

Zahniser, Mark S.↗

Comparison of TOMS and AVHRR imagery of volcanic clouds

This project consisted of merging volcanic cloud data from initial studies from TOMS and AVHRR sensors. Because of the different data acquisition platforms and processing algorithms and formats, the combination of the two data required special consideration. Once the registration technique was perfected, several eruptions with data from both sensors were studied. The conclusion showed that, from the initial work, the positions of the volcanic clouds as detected by the two sensors are very similar. Because the AVHRR algorithm is now capable of retrieving masses of ash and sulfate aerosol, the capability of comparing data from the two sensors now allows changes in SO2, H2SO4, and silicated ash in drifting clouds to be described. The results of this study culminated in several presentations, and a master's thesis, which in turn was converted into a paper submitted to the Journal of Geophysical Research. Abstracts of two presentations are attached.

Rose, William I.↗

The sensitivity of tropospheric chemistry to cloud interactions

Clouds, although only occupying a relatively small fraction of the troposphere volume, can have a substantial impact on the chemistry of the troposphere. In newly formed clouds, or in clouds with air rapidly flowing through, the chemistry is expected to be far more active than in aged clouds with stagnant air. Thus, frequent cycling of air through shortlived clouds, i.e. cumulus clouds, is likely to be a much more efficient media for altering the composition of the atmosphere than an extensive cloud cover i.e. frontal cloud systems. The impact of clouds is tested out in a 2-D channel model encircling the globe in a latitudinal belt from 30 to 60 deg N. The model contains a detailed gas phase chemistry. In addition physiochemical interactions between the gas and aqueous phases are included. For species as H2O2, CH2O, O3, and SO2, Henry's law equilibria are assumed, whereas HNO3 and H2SO4 are regarded as completed dissolved in the aqueous phase. Absorption of HO2 and OH is assumed to be mass-transport limited. The chemistry of the aqueous phase is characterized by rapid cycling of odd hydrogen, (H2O2, HO2, and OH). O2(-) (produced through dissociation of HO2) reacting with dissolved O3 is a major source of OH in the aqueous phase. This reaction can be a significant sink for O3 in the troposphere. In the interstitial cloud air, odd hydrogen is depleted, whereas NO(x) remains in the gas phase, thus reducing ozone production due to the reaction between NO and HO2. Our calculations give markedly lower ozone levels when cloud interactions are included. This may in part explain the overpredictions of ozone levels often experienced in models neglecting cloud chemical interactions. In the present study, the existence of clouds, cloud types, and their lifetimes are modeled as pseudo random variables. Such pseudo random sequences are in reality deterministic and may, given the same starting values, be reproduced. The effects of cloud interactions on the overall chemistry of the troposphere are discussed. In particular, tests are performed to determine the sensitivity of cloud frequencies and cloud types.

Jonson, Jan E.↗

Quantitative understanding of the cycles of oxidized and reduced sulfur on Venus

The evolution of the Venus atmosphere is determined by the supply of gases from the interior of the planet and outer space, and by the loss of particles to space over time. In particular, questions pertaining to the initial inventory of water and the current and past rates of outgassing can be addressed by studying the loss rates of H, D, He3 and He4. The photochemistry of the H2SO4 clouds may also have played an important role in regulating the amount of water above the cloud tops, and hence limit the rate of escape of hydrogen from the planet. Thus the problems of evolution and chemistry are intimately related. In our proposal the principal tasks we undertook to advance our understanding of the origin and evolution of water on Venus included: (1) escape of light atoms from Venus and (2) develop a photochemical model of sulfate formation. In the last two years we have made progress on Task 1 regarding how light atoms can escape from the exosphere of Venus with the development of a Monte Carlo program and in Task 2 have developed a thorough update on the SO2 photochemistry that had been previously carried out.

Yung, Yuk L.↗