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At least 397 records · Page 22

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.↗

Particle chemistry impactor experiment

Polar stratospheric cloud (PSC) particles are collected on impactors and studied with regard to physical and chemical properties to help explain the importance of heterogeneous chemical reactions for stratospheric ozone depletion. The nitric, hydrochloric, and sulfuric acid content of stratospheric aerosol particles collected at 18 km altitude was determined. It is suggested that nitric acid is a component of polar stratospheric clouds. This is important for two reasons: (1) it proves that chlorine activation takes place at the surface of PSC particles by converting chemically inert chlorine nitrate to chlorine radicals that can react with ozone; and (2) if the PSC particles are large enough to settle out from the stratosphere, the possibility of nitric acid removal can result in the denitrification of the stratosphere.

Pueschel, R. F.↗

Stratospheric Backscatter, Extinction, and Lidar Ratio Profiling After the Mt. Pinatubo Eruptions

Since August 1991 the stratospheric aerosol layer is continuously monitored with a combination Raman elastic-backscatter lidar, groundbased systems. XeCl excimer laser is used as the radiation source. Signals elastically backscattered from air molecules and particles and inelastically Raman backscattered from nitrogen molecules are detected. The measurements of these two signal profiles up to 35 km height allows the separate and independent determination of aerosol extinction and backscatter properties in the perturbed lower stratosphere. The extinction coefficient is derived from the nitrogen Raman signal profile, while the backscatter coefficient is obtained from the elastic-to-inelastic backscatter signal ratio. In this way, also the extinction-to-backscatter, or lidar, ratio profile is determined. For the first time, lidar ratios are determined in the perturbed stratospheric layer by the use of remote sensing only. The lidar ratio contains information about the size range of the stratospheric particles which are assumed to be sulfuric acid droplets, and it is needed in the calculation of aerosol optical properties from data taken with a typical backscatter lidar.

Ansmann, Albert↗

Atmospheric nuclei in the remote free-troposphere

An extensive flight series to survey aerosol present in the upper-troposphere was undertaken aboard the NASA DC-8 as part of the Global Backscatter Experiment. Aerosol with diameters greater than 3 nm were counted and sized with a combination of condensation nuclei counters and optical particle counters. Aerosol number and mass concentrations were separately identified with regard to both refractory and volatile components. Regions of the free-troposphere with the lowest mass concentrations were generally found to have the highest number concentrations and appeared to be effective regions for new particle production. These new particle concentrations appear inversely related to available aerosol surface area, and their volatility suggests a sulfuric acid composition. The long lifetime of these new particles aloft can result in their growth to sizes effective as CN and CCN that can be mixed throughout the troposphere.

Clarke, Antony D.↗

Catastrophic loss of stratospheric ozone in dense volcanic clouds

Rapid, localized loss of ozone is predicted to occur in the midlatitude and tropical stratosphere in the presence of very large concentrations of sulfate aerosols. Volcanic eruptions can increase the effective surface area of sulfuric acid so that heterogeneous reactions involving ClONO2, and secondarily N2O5, are able to suppress NO(x) abundances by more than a factor of 10 relative to gas phase chemistry. When NO(x) levels fall below a threshold, e.g., 0.6 ppb at 24 km in mid-latitudes, the chlorine-catalyzed loss of O3 proceeds at rates comparable to those during the formation of the Antarctic ozone hole, more than 50 ppb per day. If such losses occurred following the eruption of Mount Pinatubo in the most volcanically perturbed regions over the tropics and mid-latitudes, this model predicts that they are driven primarily by the suppression of NO(x) below these critical levels. The increase in stratospheric chlorine since El Chichon has made Mount Pinatubo more than twice as effective in causing rapid O3 loss.

Prather, Michael↗

The potential effects of volcanic aerosols on cirrus cloud microphysics

The potential impact of volcanic aerosols on nucleation of ice crystals in upper tropospheric cirrus clouds is examined from a microphysical perspective. The sulfuric acid aerosols which form in the stratosphere are presumably transported into the troposphere by sedimentation and tropopause folding. The tropospheric volcanic aerosol size distribution is estimated from 10-micron lidar backscatter and in situ measurements. Microphysical simulations suggest that at temperatures below about -50 C the concentration of ice crystals which nucleate may be as much as a factor of 5 larger when volcanic aerosols are present. The simulations suggest that the presence of volcanic aerosols may increase the net radiative forcing (surface warming) of certain types of cirrus near the tropopause by as much as 8 W/sq m. Further observations are required to determine whether these effects actually occur, and their global impact.

Jensen, Eric J.↗

Thermal-Control Coatings Evaluated

Report describes tests of variety of thermal-control coating materials, including white paints, second-surface-metalized fluorinated ethylene propylene, aluminum anodized in sulfuric acid, and plasma-sprayed alumina.

Dever, Joyce A.↗

SO2 on Venus: A final cross-calibration with Pioneer Venus

In our previous report, we noted that we had successfully completed all of the IUE observations which were proposed. A total of 7 Venus spectra were obtained. In the present reporting period, essentially all of the associated data reduction and analysis activities were completed, and Drs. Stern, Barker, and Na met to collaborate on data interpretation. The model atmosphere used in this analysis is similar to the one used in the analysis of the Pioneer Venus observations (Esposito, et al. 1979, 1988) and the previous IUE observations (Na, et al. 1990). In this model, sulfuric acid aerosols with a radius of about 1 micron are mixed uniformly with Rayleigh scattering gases throughout the cloud layer. There are two wavelength-independent absorbers. First, the aerosols are assumed to have a single scattering albedo of 0.98, and second a pure absorbing layer with an optical depth of 0.2 is added at an altitude of 75 mbar. The variable parameters in this model are the mixing ratios of SO2 at the cloud top (40 mbar level), and the scale height of SO2 at the same altitude. Model spectra were calculated using a radiative transfer code utilizing a Markov Chain method. Each model calculation takes into account the multiple scattering and the vertical inhomogeneity of the atmosphere. We reported those initial results at the 1992 meeting of the AAS Division of Planetary Sciences (Barker, Stern, and Na 1992) The important finding we have reached is that the 1991 IUE observations indicate that the long-term decline in Venus SO2 abundance has either halted or reversed. Our simultaneous groundbased measurements made on the McDonald Observatory 2.7 m corroborate this result. We are now preparing a paper describing these IUE results for publication in Icarus. With the IUE results reduced, we are also beginning a project to compare the 1991 IUE results to Pioneer Venus UV spectra made on the same dates.

Stern, S. Alan↗

Understanding the variation in the millimeter-wave emission of Venus

Recent observations of the millimeter-wave emission from Venus at 112 GHz (2.6 mm) have shown significant variations in the continuum flux emission that may be attributed to the variability in the abundances of absorbing constituents in the Venus atmosphere. Such constituents include gaseous H2SO4, SO2, and liquid sulfuric acid (cloud condensates). Recently, Fahd and Steffes have shown that the effects of liquid H, SO4, and gaseous SO2 cannot completely account for this measured variability in the millimeter-wave emission of Venus. Thus, it is necessary to study the effect of gaseous H2SO4 on the millimeter-wave emission of Venus. This requires knowledge of the millimeter-wavelength (MMW) opacity of gaseous H2SO4, which unfortunately has never been determined for Venus-like conditions. We have measured the opacity of gaseous H2SO4 in a CO2 atmosphere at 550, 570, and 590 K, at 1 and 2 atm total pressure, and at a frequency of 94.1 GHz. Our results, in addition to previous centimeter-wavelength results are used to verify a modeling formalism for calculating the expected opacity of this gaseous mixture at other frequencies. This formalism is incorporated into a radiative transfer model to study the effect of gaseous H2SO4 on the MMW emission of Venus.

Fahd, Antoine K.↗

Groundbased near-IR observations of the surface of Venus

We present images of the nightside of Venus taken in the near-infrared windows at 1.0, 1.1, 1.18, 1.28, 1.31, and 2.3 microns with the new infrared camera/spectrometer IRIS on the Anglo-Australian Telescope. These data were taken in spectral-mapping mode. This technique involves scanning the telescope perpendicular to the slit, while collecting spectra at successive slit positions across the planet. We produce data cubes with one spectral and two spatial dimensions. Images can be extracted over any wavelength regions. Each image has square pixels of 0.8 inch resolution. We reduced the scattered light from the sunlit crescent in images extracted from each window by subtracting images taken on either side of the window, where the Venus atmosphere is opaque. Unlike the short wavelength windows, which reveal thermal contrasts that originate primarily from the surface and deep atmosphere, the emission in the 2.3 microns window is produced at much higher altitudes (30-40 km). Emission contrasts seen near 2.3 microns are associated with horizontal variations in the cloud optical depths, and have rotation periods of about six days. We detect large contrasts in infrared emission (20-40 percent) across the disc of Venus in the 1.0-, 1.1-, 1.18-, 1.28-, and 1.31-micron images. Contrasts at these wavelengths may be due to a combination of variations in the optical depths of the overlying sulfuric acid clouds and differences in surface emission. Comparison with the 2.3-micron images show that the patterns seen in the 1.28- and 1.31-micron windows are consistent with cloud optical depth variations alone and require no contribution from the surface. However, images at 1.0, 1.1, and 1.8 microns from July 1991 show a dark feature having a contrast that increases with decreasing wavelength. This behavior is contrary to that expected of cloud absorption. Images taken on three successive days in October show another dark feature that is stationary with respect to the surface. These regions of lower emission correspond closely to the high-altitude surface regions of Beta Regio and Aphrodite Terra. The images can potentially reveal the near-infrared emissiveity of the surface of Venus, thereby complementing Magellan radar reflectivity and ground based radio emissivity measurements. The contrast ratio between highlands and plains is much smaller than would be expected for blackbody radiation from the surface along. Unlike at radio wavelengths, where the atmosphere is essentially transparent, at near-infrared wavelengths the atmosphere emits, absorbs, and scatters radiation, and can modify the observed topographically induced contrasts. The additional radiation from the atmosphere reduces the contrast, and further modification would be expected if terrain at different altitudes has different emissivities. A fit to our data therefore requires, and may constrain, a model of the lowest scale height of the atmosphere.

Meadows, V. S.↗

UPT scenarios: Implications for system reliability

The objective of this project was to examine the corrosion resistance of 316L stainless steel in several urine pre-treat solutions. Four solutions were examined: untreated urine (control); urine pretreated with oxone (potassium peroxymonosulfate sulfate); urine pretreated with sodium hypochlorite (NaOCl); and urine pretreated with ozone (O3). In accordance with current procedures, all solutions but the control were acidified to a pH of 2.5 using sulfuric acid--this suppresses the generation of ammonia in the solutions and is intended to limit microbial growth. Welded and unwelded coupons were exposed to each solution. In addition, Titanium coupons (welded and unwelded) were exposed to biologically active environmental control and life support system (ECLSS) water. Microbial attachment and biofilm growth were monitored. Ozone was examined as a biocide/oxidizer/corrosion preventative (simultaneous addition) and as a remediation method (added one week after exposure). In an unrelated effort, HP 9-4-30 coupons were exposed to biologically active solutions. Corrosion rates for welded and unwelded samples were determined--results were correlated to the ongoing HP 9-4-30 weldment stress corrosion study.

Walsh, Daniel W.↗

Method for producing oxygen from lunar materials

This invention is related to producing oxygen from lunar or Martian materials, particularly from lunar ilmenite in situ. The process includes producing a slurry of the minerals and hot sulfuric acid, the acid and minerals reacting to form sulfates of the metal. Water is added to the slurry to dissolve the minerals into an aqueous solution, the first aqueous solution is separated from unreacted minerals from the slurry, and the aqueous solution is electrolyzed to produce the metal and oxygen.

Sullivan, Thomas A.↗

Tropical ozone loss following the eruption of Mt. Pinatubo

Total Ozone Mapping Spectrometer (TOMS) measurements of equatorial total ozone following the eruption of Mt. Pinatubo show a decrease of up to 6 percent over climatology. Ozone losses begin approximately a month following the eruption, consistent with the time required for the SO2 to convert to sulfuric acid aerosol. The thick aerosol layer interferes with the TOMS retrieval, but this interference is small and easily accounted for in the retrieval. Ozone values remain below climatology until December, 1991. Ozonesonde data from Natal, Brazil taken before and two months after the eruption support TOMS observations of ozone loss. These sondes show that the ozone loss region is confined to a 2-3 km thick layer between 24 and 28 km.

Schoeberl, Mark R.↗

A modified sulfate process to lunar oxygen

A modified sulfate process which produces oxygen from iron oxide-bearing minerals in lunar soil is under development. Reaction rates of ilmenite in varying strength sulfuric acid have been determined. Quantitative conversion of ilmenite to ferrous sulfate was observed over a range of temperatures and concentrations. Data has also been developed on the calcination of by-product sulfates. System engineering for overall operability and simplicity has begun, suggesting that a process separating the digestion and sulfate dissolution steps may offer an optimum process.

Sullivan, Thomas A.↗

Chemical kinetic studies of atmospheric reactions using tunable diode laser spectroscopy

IR absorption using tunable diode laser spectroscopy provides a sensitive and quantitative detection method for laboratory kinetic studies of atmospheric trace gases. Improvements in multipass cell design, real time signal processing, and computer controlled data acquisition and analysis have extended the applicability of the technique. We have developed several optical systems using off-axis resonator mirror designs which maximize path length while minimizing both the sample volume and the interference fringes inherent in conventional 'White' cells. Computerized signal processing using rapid scan (300 kHz), sweep integration with 100 percent duty cycle allows substantial noise reduction while retaining the advantages of using direct absorption for absolute absorbance measurements and simultaneous detection of multiple species. Peak heights and areas are determined by curve fitting using nonlinear least square methods. We have applied these techniques to measurements of: (1) heterogeneous uptake chemistry of atmospheric trace gases (HCl, H2O2, and N2O5) on aqueous and sulfuric acid droplets; (2) vapor pressure measurements of nitric acid and water over prototypical stratospheric aerosol (nitric acid trihydrate) surfaces; and (3) discharge flow tube kinetic studies of the HO2 radical using isotopic labeling for product channel and mechanistic analysis. Results from each of these areas demonstrate the versatility of TDL absorption spectroscopy for atmospheric chemistry applications.

Worsnop, Douglas R.↗

Stratospheric aircraft exhaust plume and wake chemistry

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 is documented. A kinetic condensation model was implemented to predict heterogeneous condensation in the plume regime behind an HSCT flying in the lower stratosphere. Simulations were performed to illustrate the parametric dependence of contrail droplet growth on the exhaust condensation nuclei number density and size distribution. Model results indicate that the condensation of water vapor is strongly dependent on the number density of activated CN. Incorporation of estimates for dilution factors into a Lagrangian box model of the far-wake regime with scale-dependent diffusion indicates negligible decrease in ozone and enhancement of water concentrations of 6-13 times background, which decrease rapidly over 1-3 days. Radiative calculations indicate a net differential cooling rate of the plume about 3K/day at the beginning of the wake regime, with a total subsidence ranging between 0.4 and 1 km. Results from the Lagrangian plume model were used to estimate the effect of repeated superposition of aircraft plumes on the concentrations of water and NO(y) along a flight corridor. Results of laboratory studies of heterogeneous chemistry are also described. Kinetics of HCl, N2O5 and ClONO2 uptake on liquid sulfuric acid were measured as a function of composition and temperature. Refined measurements of the thermodynamics of nitric acid hydrates indicate that metastable dihydrate may play a role in the nucleation of more stable trihydrates PSC's.

Miake-Lye, R. C.↗

Determination of trace elements in triglycine sulfate solutions

Ten elements were divided into 2 groups. The elements in the first group included iron, nickel, chromium, manganese, copper, and gold. The elements in the second group included zinc, cobalt, lead, cadmium, and gold. Five ppm of each element in each group was spiked in a 1 percent triglycine sulfate (TGS) solution. Glycine was removed with 1-naphthyl isocyanate in ether medium. The glycine derivative 1-naphthyl isocyanate glycine was removed by filtration, and the filtrates were analyzed for the different elements. Analysis of these elements was performed by using the 5100 Perkin-Elmer Atomic Absorption Spectrophotometer. The result of these experiments was the observation that there was a decrease in the concentration of chromium and gold, which was interpreted to be due to the chelation of these elements by the derivative 1-naphthyl isocyanate glycine. Further research is needed to determine the concentration of other elements in triglycine sulfate (TGS) solutions. These elements will include lithium, sodium, rubidium, magnesium, calcium, strontium, barium, aluminum, and silicon. These are the most likely elements to be found in the sulfuric acid used in manufacturing the TGS crystal. Moreover, we will extend our research to investigate the structural formula of the violet colored chelated compounds, which had been formed by interaction of the derivative 1-naphthyl isocyanate glycine with the different elements, such as gold, chromium.

Tadros, Shawky H.↗

Examination of the observed synoptic scale cirrus cloud environment: The December 3-6 FIRE cirrus case study

Recently, Sassen provided evidence for supercooled water droplets in cirrus uncinus cell heads at temperatures between 40 and -50 C. Chemistry related to volcanic aerosol of stratospheric origin was evoked as an explanation for this phenomenon. Sassen speculated that injections of sulfuric acid droplets into the upper troposphere were accomplished by tropopause folds associated with subtropical jet streams. He also postulated global climatic perturbations due to the effect of these cirrus microphysical perturbations on radiative fluxes. Using data processing and objective analysis techniques described by Mace and Ackerman, the synoptic scale environment was examined for evidence of tropopause folds that may have served as a source mechanism of stratospheric aerosol in the upper troposphere.

Mace, Gerald G.↗