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At least 145 records · Page 8

Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

Singh, J. J.↗

A determination of the composition of the Venus clouds from aircraft observations in the near infrared

Summary of the evidence showing that the first optical depth of the Venus cloud layer is composed of a water solution of sulfuric acid, including earlier aircraft observations of Venus' reflectivity in the region from 1 to 4 microns obtained at a phase angle of 120 deg. Analyses of these aircraft results indicated that of all the proposed cloud candidates only a sulfuric acid solution with a concentration of 75% or more H2SO4 by weight was consistent with the observed 3-micron cloud feature. Aircraft observations of Venus are presented which were obtained in the same spectral region at a phase angle of 40 deg and in the region from 3 to 6 microns at a phase angle of 136 deg. Comparing the two sets of observations in the region from 1 to 4 microns, a striking phase effect is found: the reflectivity is much lower in the 3-micron region and there is a much more marked decline between 1.3 and 2.5 microns for the data obtained at the smaller phase angle. The observations made at the 40-deg phase angle are consistent with the theoretical behavior of a sulfuric acid cloud and imply that the sulfuric acid is present to at least many tens of optical depth below the cloud tops. Arguments concerning the concentration of the solution are reviewed, and it is concluded that the best current estimate is about 85% H2SO4 by weight.

Pollack, J. B.↗

Latitudinal distribution of black carbon soot in the upper troposphere and lower stratosphere

Black carbon soot from the upper troposphere and lower stratosphere has been systematically collected at latitudes from 90 deg N to 45 deg S. The measured latitudinal distribution of this soot at 10 to 11 km altitude is found to covary with commercial air traffic fuel use, suggesting that aircraft fuel combustion at altitude is the principal source. In addition, at latitudes where the commercial air traffic is high, measured black carbon soot values are high even at 20 km altitude, suggesting that aircraft-generated soot injected just above the tropopause may be transported to higher altitudes. During the volcanically influenced period in which these samples were collected, the number abundances, total mass, and calculated total surface area of black carbon soot are 2-3 orders of magnitude lower than similar measures of sulfuric acid aerosol. During volcanically quiescent periods, the calculated total surface area of black carbon soot aerosol is of the same order of magnitude as that of the background sulfuric acid aerosol. It appears from this comparison that black carbon soot is only capable of influencing lower stratosphere or upper troposphere chemistry during periods when the aerosol budget is not dominated by volcanic activity. It remains to determine the extent to which black carbon soot particles act as nuclei for sulfuric acid aerosol formation. However, mass balance calculations suggest that aircraft soot injected at altitude does not represent a significant source of condensation nuclei for sulfuric acid aerosols.

Blake, David F.↗

Evidence for an elemental sulfur component of the clouds from Venus spectrophotometry

The decrease in the reflectivity of Venus in the near-UV can be explained if the clouds contain particles of elemental sulfur in addition to sulfuric acid. The low-resolution McDonald-Pittsburgh spectrum can be fitted by two sulfur-containing, multiple-scattering cloud models: (1) a mixed cloud consisting of one particle of elemental sulfur of radius 10 microns for every 670 particles of sulfuric acid of radius 1 micron, and (2) a layered cloud of optical thickness tau = 1.0 consisting of one-micron particles of sulfuric acid overlying a thick cloud of elemental sulfur particles of radius 3.6 microns. Some of the sulfur is incompletely polymerized. The source of the sulfur is photo-dissociation of COS, although some may also be recycled from the lower atmosphere. The sulfur plays a crucial role in the planetary meteorology of Venus since it is responsible for the bulk of the absorption of solar energy.

Hapke, B.↗

Microbiological test results using three urine pretreatment regimes with 316L stainless steel

Three urine pretreatments, (1) Oxone (Dupont) and sulfuric acid, (2) sodium hypochlorite and sulfuric acid, (3) and ozone, were studied for their ability to reduce microbial levels in urine and minimize surface attachment to 316L stainless steel coupons. Urine samples inoculated with Bacillus insolitus and a filamentous mold, organisms previously recovered from the vapor compression distillation subsystem of NASA Space Station Freedom water recovery test were tested in glass corrosion cells containing base or weld metal coupons. Microbial levels, changes in pH, color, turbidity, and odor of the fluid were monitored over the course of the 21-day test. Specimen surfaces were examined by scanning electron microscopy at completion of the test for microbial attachment. Ozonated urine samples were less turbid and had lower microbial levels than controls or samples receiving other pretreatments. Base metal coupons receiving pretreatment were relatively free of attached bacteria. However, well-developed biofilms were found in the heat-affected regions of welded coupons receiving Oxone and hypochlorite pretreatments. Few bacteria were observed in the same regions of the ozone pretreatment sample.

Huff, Timothy L.↗

Reduction and analysis of seasons 15 and 16 (1991 - 1992) Pioneer Venus radio occultation data and correlative studies with observations of the near-infrared emission of Venus

Radio occultation experiments, and radio astronomical observations have suggested that significant variations (both spatial and temporal) in the abundances of sulfur-bearing gases are occurring below the Venus cloud layers. In addition, recent Near Infra-Red images of the nightside of Venus revealed large-scale features which sustain their shape over multiple rotations (the rotation periods of the features are 6.0 +/- 0.5 days). Presumably, the contrast variations in the NIR images are caused by variations in the abundance of large particles in the cloud deck. If these particles are composed of liquid sulfuric acid, one would expect a strong anticorrelation between regions with a high abundance of sulfuric acid vapor, and regions where there are large particles. One technique for monitoring the abundance and distribution of sulfuric acid vapor (H2SO4) at and below the main Venus cloud layer (altitudes below 50 km) is to measure the 13-cm wavelength opacity using Pioneer Venus Orbiter Radio Occultation Studies (PV-ORO). We are working to characterize variations in the abundance and distribution of subcloud H2SO4(g) in the Venus atmosphere by using a number of 13-cm radio occultation measurements conducted with the Pioneer Venus Orbiter near the inferior conjunction of 1991. When retrieved, the vertical profiles of the abundance of H2SO4(g) will be compared and correlated with NIR images of the night side of Venus made during the same period of time. Hopefully, the combination of these two different types of data will make it possible to constrain or identify the composition of the large particles causing the features observed in the NIR images. Considered on their own, however, the parameters retrieved from the radio occultation experiments are valuable science products.

Jenkins, Jon M.↗

Uptake of Organic Vapors by Sulfate Aerosols: Physical and Chemical Processes

While it is known that upper tropospheric sulfate particles contain a significant amount of organic matter, both the source of the organic fraction and its form in solution are unknown. These studies explore how the chemical characteristics of the molecules and surfaces in question affect heterogeneous interactions. The solubilities of acetaldehyde [CH3CHO] and ethanol [CH3CH20H] in cold, aqueous sulfuric acid solutions have been measured by Knudsen cell studies. Henry's law solubility coefficients range from 10(exp 2) to 10(exp 5) M/atm for acetaldehyde, and from 10(exp 4) to 10(exp 9) M/atm for ethanol under upper tropospheric conditions (210-240 K, 40-80 wt. % H2S04). The multiple solvation pathways (protonation, enolization, etc.) available to these compounds in acidic aqueous environments will be discussed. Preliminary results from the interaction of acetaldehyde with solutions of formaldehyde in sulfuric acid will be presented as well. The physical and chemical processes that affect organic uptake by aqueous aerosols will be explored, with the aim of evaluating organic species not yet studied in low temperature aqueous sulfuric acid.

Michelsen, R. R.↗

Chemical analysis of aerosol in the Venusian cloud layer by reaction gas chromatography on board the Vega landers

The experiment on sulfuric acid aerosol determination in the Venusian cloud layer on board the Vega landers is described. An average content of sulfuric acid of approximately 1 mg/cu m was found for the samples taken from the atmosphere at heights from 63 to 48 km and analyzed with the SIGMA-3 chromatograph. Sulfur dioxide (SO2) was revealed in the gaseous sample at the height of 48 km. From the experimental results and blank run measurements, a suggestion is made that the Venusian cloud layer aerosol consists of more complicated particles than the sulfuric acid water solution does.

Gelman, B. G.↗

Stratospheric aerosol properties and their effects on infrared radiation.

This paper presents a stratospheric aerosol model and infers its effects on terrestrial radiation. Composition of the aerosol is assumed to be concentrated sulfuric acid. An appropriate size distribution has been determined from available size distribution measurements of other investigators. Aerosols composed of concentrated sulfuric acid emit energy in the atmospheric window region of the infrared spectrum, 8-13 microns. Laboratory measurements of optical constant data obtained at room temperature are presented for 75 and 90% aqueous sulfuric acid. Calculations of an aerosol extinction coefficient are then performed by using the above data. Effects of changes in aerosol phase and temperature are discussed but not resolved.

Remsberg, E. E.↗

Liquid content of the lower clouds of Venus as determined from Mariner 10 radio occultation

S- and X-band radio occulation data obtained during the Mariner 10 flyby of Venus are analyzed to determine the effects of signal attenuation due to the clouds of Venus. The signal-amplitude data are corrected for errors introduced by spacecraft motion and antenna steering during the occultation, absorption-coefficient profiles are computed, and the liquid content of the Venusian clouds is estimated. Excess attenuation effects are found and ascribed to absorption by small liquid particles, consisting of a water-sulfuric acid mixture containing 75% + or - 25% sulfuric acid, in the clouds. Three absorbing cloud layers at respective heights of 68, 60, and 48 km are suggested by the X-band absorptivity profile, but only the 68- and 48-km layers are clearly indicated by the S-band profile. The relatively slow S-band absorption at 60 km is tentatively attributed to an unknown constituent that is much more absorbing in the X-band than in the S-band. The results are compared with nephelometer measurements performed at 0.9 micron by the Venera 9 and 10 probes.

Kliore, A. J.↗

Solid film lubricants and thermal control coatings flown aboard the EOIM-3 MDA sub-experiment

Additional experimental data were desired to support the selection of candidate thermal control coatings and solid film lubricants for the McDonnell Douglas Aerospace (MDA) Space Station hardware. The third Evaluation of Oxygen Interactions With Materials Mission (EOIM-3) flight experiment presented an opportunity to study the effects of the low Earth orbit environment on thermal control coatings and solid film lubricants. MDA provided five solid film lubricants and two anodic thermal control coatings for EOIM-3. The lubricant sample set consisted of three solid film lubricants with organic binders one solid film lubricant with an inorganic binder, and one solid film lubricant with no binder. The anodize coating sample set consisted of undyed sulfuric acid anodize and cobalt sulfide dyed sulfuric acid anodize, each on two different substrate aluminum alloys. The organic and inorganic binders in the solid film lubricants experienced erosion, and the lubricating pigments experienced oxidation. MDA is continuing to assess the effect of exposure to the low Earth orbit environment on the life and friction properties of the lubricants. Results to date support the design practice of shielding solid film lubricants from the low Earth orbit environment. Post-flight optical property analysis of the anodized specimens indicated that there were limited contamination effects and some atomic oxygen and ultraviolet radiation effects. These effects appeared to be within the values predicted by simulated ground testing and analysis of these materials, and they were different for each coating and substrate.

Murphy, Taylor J.↗

Light Absorption of Stratospheric Aerosols: Long-Term Trend and Contribution by Aircraft

Measurements of aerosol light-absorption coefficients are useful for studies of radiative transfer and heating rates. Ogren appears to have published the first light- absorption coefficients in the stratosphere in 1981, followed by Clarke in 1983 and Pueschel in 1992. Because most stratospheric soot appears to be due to aircraft operations, application of an aircraft soot aerosol emission index to projected fuel consumption suggests a threefold increase of soot loading and light absorption by 2025. Together, those four data sets indicate an increase in mid-visible light extinction at a rate of 6 % per year. This trend is similar to the increase per year of sulfuric acid aerosol and of commercial fleet size. The proportionality between stepped-up aircraft operations above the tropopause and increases in stratospheric soot and sulfuric acid aerosol implicate aircraft as a source of stratospheric pollution. Because the strongly light-absorbing soot and the predominantly light-scattering sulfuric acid aerosol increase at similar rates, however, the mid-visible stratospheric aerosol single scatter albedo is expected to remain constant and not approach a critical value of 0.98 at which stratospheric cooling could change to warming.

Pueschel , R. F.↗

Balloon for Long-Duration, High-Altitude Flight at Venus

A document describes a 5.5-m-diameter, helium-filled balloon designed for carrying a scientific payload having a mass of 44 kg for at least six days at an altitude of about 55 km in the atmosphere of Venus. The requirement for floating at nearly constant altitude dictates the choice of a mass-efficient spherical super-pressure balloon that tracks a constant atmospheric density. Therefore, the balloon is of a conventional spherical super-pressure type, except that it is made of materials chosen to minimize solar radiant heating and withstand the corrosive sulfuric acid aerosol of the Venusian atmosphere. The shell consists of 16 gores of a multilayer composite material. The outer layer, made of polytetrafluoroethylene, protects against sulfuric acid aerosol. Next is an aluminum layer that reflects sunlight to minimize heating, followed by an aluminized polyethylene terephthalate layer that resists permeation by helium, followed by an aromatic polyester fabric that imparts strength to withstand deployment forces and steady super-pressure. A polyurethane coat on the inner surface of the fabric facilitates sealing at gore-to-gore seams. End fittings and seals, and a tether connecting the end fittings to a gondola, are all made of sulfuric-acid-resistant materials.

Hall, Jeffrey↗

Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

Iraci, Laura T.↗

High Altitude Venus Operational Concept (HAVOC): Proofs of Concept

The atmosphere of Venus is an exciting destination for both further scientific study and future human exploration. A recent internal NASA study of a High Altitude Venus Operational Concept (HAVOC) led to the development of an evolutionary program for the exploration of Venus, with focus on the mission architecture and vehicle concept for a 30-day crewed mission into Venus's atmosphere at 50 kilometers. Key technical challenges for the mission include performing the aerocapture maneuvers at Venus and Earth, inserting and inflating the airship at Venus during the entry sequence, and protecting the solar panels and structure from the sulfuric acid in the atmosphere. Two proofs of concept were identified that would aid in addressing some of the key technical challenges. To mitigate the threat posed by the sulfuric acid ambient in the atmosphere of Venus, a material was needed that could protect the systems while being lightweight and not inhibiting the performance of the solar panels. The first proof of concept identified candidate materials and evaluated them, finding FEP-Teflon (Fluorinated Ethylene Propylene-Teflon) to maintain 90 percent transmittance to relevant spectra even after 30 days of immersion in concentrated sulfuric acid. The second proof of concept developed and verified a packaging algorithm for the airship envelope to inform the entry, descent, and inflation analysis.

Jones, Christopher A.↗

Aircraft observations of Venus' near-infrared reflection spectrum - Implications for cloud composition

A comparison of aircraft-based measurement data on Venus' near-infrared (1.2- to 4.1-micron) reflection spectrum with computer generated spectra of a number of cloud candidates shows a 75-% or more concentrated water solution of sulfuric acid to give the only acceptable match to the profile of Venus' strong 3-micron absorption feature. However, the measurement data obtained also show a modest decline in reflectivity from 2.3-micron to 1.2-micron wavelength, which is inconsistent with the flat spectrum of sulfuric acid in this spectral region. It is hypothesized that this decline is due to impurities in the sulfuric acid droplets.

Pollack, J. B.↗

Solubility of HOBr in Acidic Solution and Implications for Liberation of Halogens Via Aerosol Processing

Halogen species are known to catalytically destroy ozone in several regions of the atmosphere. In addition to direct catalytic losses, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr) is a key species in the linkage of BrOx to ClOx and HOx. The aqueous- phase coupling reaction HOBr + HCI (right arrow) BrCl + H2O may provide a pathway for chlorine activation on sulfate aerosols at temperatures warmer than those required for polar stratospheric cloud formation. We have measured t h e solubility of HOBr in 45 - 70 wt% sulfuric acid solutions. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, H* = 10(exp 4) - 10(exp 7) mol dm(exp -3) atm(exp -1). The expected inverse dependence of H* on temperature was observed, but only a weak dependence on acidity was found. The solubility of HOBr is comparable to that of HBr, indicating that equilibrium concentrations of HOBr could equal or exceed those of HBr in upper tropospheric and lower stratospheric aerosols. Despite the high solubility of HOBr, aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Our measurements of HOBr uptake in aqueous sulfuric acid in the presence of other brominated gases show the evolution of gaseous products including Br2O and Br2.

Iraci, Laura T.↗

Production of hydrogen by electron transfer catalysis using conventional and photochemical means

Alternate methods of generating hydrogen from the sulfuric acid thermal or electrochemical cycles are presented. A number of processes requiring chemical, electrochemical or photochemical methods are also presented. These include the design of potential photoelectrodes and photocatalytic membranes using Ru impregnated nafion tubing, and the design of experiments to study the catalyzed electrolytic formation of hydrogen and sulfuric acid from sulfur dioxide and water using quinones as catalysts. Experiments are carried out to determine the value of these approaches to energy conversion.

Rillema, D. P.↗