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At least 19 records

HCl in rocket exhaust clouds - Atmospheric dispersion, acid aerosol characteristics, and acid rain deposition

Both measurements and model calculations of the temporal dispersion of peak HCl (g + aq) concentration in Titan III exhaust clouds are found to be well characterized by one-term power-law decay expressions. The respective coefficients and decay exponents, however, are found to vary widely with meteorology. The HCl (g), HCl (g + aq), dewpoint, and temperature-pressure-altitude data for Titan III exhaust clouds are consistent with accurately calculated HCl/H2O vapor-liquid compositions for a model quasi-equilibrated flat surface aqueous aerosol. Some cloud evolution characteristics are also defined. Rapid and extensive condensation of aqueous acid clearly occurs during the first three min of cloud rise. Condensation is found to be intensified by the initial entrainment of relatively moist ambient air from lower levels, that is, from levels below eventual cloud stabilization. It is pointed out that if subsequent dilution air at stabilization altitude is significantly drier, a state of maximum condensation soon occurs, followed by an aerosol evaporation phase.

Pellett, G. L.↗

Nitric acid aerosols at the tropical tropopause

It is thermodynamically possible for nitric acid aerosol particles to form in the lower stratosphere and upper troposphere in tropical latitudes. This aerosol would have essentially the same composition as the polar stratospheric clouds observed in the winter polar stratosphere. Calculations have been carried out, indicating that nitric acid aerosols may form at the same altitudes as layers observed in the tropics by the SAGE satellite system.

Hamill, Patrick↗

Venus -Mesospheric hazes of ice, dust, and acid aerosols

Four distinct types of particles are suggested to be present in the upper atmosphere of Venus. The lowest and densest haze may consist of a submicron sulfuric acid aerosol which extends above the cloud tops, up to about 80 km, representing an extension of the upper cloud deck. Temperature structure measurements in the 70-120 km altitude range indicate the occasional appearance of two independent water ice layers, of which the lower may form between 80 and 100 km and is probably the detached haze layer noted in high contrast limb photography. A nucleation of this ice layer on sulfuric acid aerosols is hypothesized. Temperatures of the Venus mesopause, near 120 km altitude, are frequently cold enough to allow ice nucleation on meteoric dust or ambient ions, yielding a haze (analogous to noctilucent clouds on earth) which is expected to be tenuous to the point of optical invisibility.

Turco, R. P.↗

Modeling of growth and evaporation effects on the extinction of 1.0-micron solar radiation traversing stratospheric sulfuric acid aerosols

The effects of growth and evaporation of stratospheric sulfuric acid aerosols on the extinction of solar radiation traversing such an aerosol medium are reported for the case of 1.0-micron solar radiation. Modeling results show that aerosol extinction is not very sensitive to the change of ambient water vapor concentration, but is sensitive to ambient temperature changes, especially at low ambient temperatures and high ambient water vapor concentration. A clarification is given of the effects of initial aerosol size distribution and composition on the change of aerosol extinction due to growth and evaporation processes. It is shown that experiments designed to observe solar radiation extinction of aerosols may also be applied to the determination of observed changes in aerosol optical properties, environmental parameters, or the physical and optical characteristics of sulfate aerosols.

Yue, G. K.↗

Hydrochloric acid aerosol formation by the interaction of hydrogen chloride with humid air

The conditions in which hydrochloric acid aerosol is predicted by the interaction of hydrogen chloride gas with the water vapor in humid air are analyzed. The liquid gas phase equilibrium for the HCL-H2O system is expressed in terms of relative humidity and hydrogen chloride concentration as parts per million, units commonly used in pollution studies. Presented are the concentration (wt %) of HC1 in the aerosol and the concentration of aerosol (ppm) predicted.

Rhein, R. A.↗

Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

Baldwin, A. C.↗

Hydrochloric acid aerosol and gaseous hydrogen chloride partitioning in a cloud contaminated by solid rocket exhaust

Partitioning of hydrogen chloride between hydrochloric acid aerosol and gaseous HCl in the lower atmosphere was experimentally investigated in a solid rocket exhaust cloud diluted with humid ambient air. Airborne measurements were obtained of gaseous HCl, total HCl, relative humidity and temperature to evaluate the conditions under which aerosol formation occurs in the troposphere in the presence of hygroscopic HCl vapor. Equilibrium predictions of HCl aerosol formation accurately predict the measured HCl partitioning over a range of total HCl concentrations from 0.6 to 16 ppm.

Sebacher, D. I.↗

Chemical Transport Models Often Underestimate Inorganic Atmospheric Aerosol Acidity in Remote Regions of the Atmosphere

The inorganic fraction of fine particles affects numerous physicochemical processes in the atmosphere. However, there is large uncertainty in its burden and composition due to limited global measurements. Here, we present observations from eleven different aircraft campaigns from around the globe and investigate how aerosol pH and ammonium balance change from polluted to remote regions, such as over the oceans. Both parameters show increasing acidity with remoteness, at all altitudes, with pH decreasing from about 3 to about -1 and ammonium balance decreasing from almost 1 to nearly 0. We compare these observations against nine widely used chemical transport models and find that the simulations show more scatter (generally R(exp 2) < 0.50) and typically predict less acidic aerosol in the most remote regions. These differences in observations and predictions are likely to result in underestimating the model-predicted direct radiative cooling effect for sulfate, nitrate, and ammonium aerosol by 15-39%.

Chemical transport model↗

FTIR studies of low temperature sulfuric acid aerosols

Sub-micrometer sized sulfuric acid H2SO4 particles were generated using a constant output atomizer source. The particles were then exposed to water vapor before being injected into a low temperature cell. Multipass transmission Fourier Transformation Infrared (FTIR) spectroscopy was used to determine the phase and composition of the aerosols as a function of time for periods of up to five hours. Binary H2SO4H2O aerosols with compositions from 35 to 95 wt % H2SO4 remained liquid for over 3 hours at room temperatures ranging from 189-240 K. These results suggest that it is very difficut to freeze SSAs via homogeneous nucleation. Attempts to form aerosols more dilute than 35 wt % H2SO4 resulted in ice formation.

Anthony, S. E.↗

Stratospheric aerosol acidity, density, and refractive index deduced from SAGE 2 and NMC temperature data

Water vapor concentrations obtained by the Stratospheric Aerosol and Gas Experiment 2 (SAGE 2) and collocated temperatures provided by the National Meteorological Center (NMC) from 1986 to 1990 are used to deduce seasonally and zonally averaged acidity, density, and refractive index of stratospheric aerosols. It is found that the weight percentage of sulfuric acid in the aerosols increases from about 60 just above the tropopause to about 86 at 35 km. The density increases from about 1.55 to 1.85 g/cu cm between the same altitude limits. Some seasonal variations of composition and density are evident at high latitudes. The refractive indices at 1.02, 0.694, and 0.532 micrometers increase, respectively, from about 1.425, 1.430, and 1.435 just above the tropopause to about 1.445, 1.455, and 1.458 at altitudes above 27 km, depending on the season and latitude. The aerosol properties presented can be used in models to study the effectiveness of heterogeneous chemistry, the mass loading of stratospheric aerosols, and the extinction and backscatter of aerosols at different wavelengths. Computed aerosol surface areas, rate coefficients for the heterogeneous reaction ClONO2 + H2O yields HOCl + HNO3 and aerosol mass concentrations before and after the Pinatubo eruption in June 1991 are shown as sample applications.

Yue, G. K.↗

Spatial variation of stratospheric aerosol acidity and model refractive index - Implications of recent results

Recent experimental results indicate that little or no solid ammonium sulfate is present in background stratospheric aerosols. Other results allow straightforward calculation of sulfuric acid/water droplet properties (acidity, specific gravity, refractive index) as functions of stratospheric temperature and humidity. These results are combined with a variety of latitudinal and seasonal temperature and humidity profiles to obtain corresponding profiles of droplet properties. These profiles are used to update a previous model of stratospheric aerosol refractive index. The new model retains the simplifying approximation of vertically constant refractive index in the inner stratosphere, but has sulfuric acid/water refractive index values that significantly exceed the previously used room temperature values. Mean conversion ratios (e.g., extinction-to-number, backscatter-to-volume) obtained using Mie scattering calculations with the new refractive indices are very similar to those obtained for the old indices, because the effects of deleting ammonium sulfate and increasing acid indices tend to cancel each other.

Russell, P. B.↗

Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

Iraci, L. T.↗

On the prolonged lifetime of the El Chichon sulfuric acid aerosol cloud

The observed decay of the aerosol mixing ratio following the eruption of El Chichon appears to have been 20-30 percent slower than that following the eruption of Fuego in 1974, even though the sulfuric acid droplets were observed to grow to considerably larger sizes after El Chichon. This suggests the possible presence of a condensation nuclei and sulfuric acid vapor source and continued growth phenomena occurring well after the El Chichon eruption. It is proposed that the source of these nuclei and the associated vapor may be derived from annual evaporation and condensation of aerosol in the high polar regions during stratospheric warming events, with subsequent spreading to lower latitudes.

Hofmann, D. J.↗

On the growth of nitric and sulfuric acid aerosol particles under stratospheric conditions

A theory for the formation of frozen aerosol particles in the Antarctic stratosphere was developed and applied to the formation of polar stratospheric clouds. The theory suggests that the condensed ice particles are composed primarily of nitric acid and water, with small admixtures of sulfuric and hydrochloric acids in solid solution. The proposed particle formation mechanism is in agreement with the magnitude and seasonal behavior of the optical extinction observed in the winter polar stratosphere.

Hamill, Patrick↗

The reaction probability of N2O5 with sulfuric acid aerosols at stratospheric temperatures and compositions

We have measured the rate of reaction of N2O5 with H2O on monodisperse, submicrometer H2SO4 particles in a low-temperature flow reactor. Measurements were carried out at temperatures between 225 K and 293 K on aerosol particles with sizes and compositions comparable to those found in the stratosphere. At 273 K, the reaction probability was found to be 0.103 +/- 0.0006, independent of H2SO4 composition from 64 to 81 wt%. At 230 K, the reaction probability increased from 0.077 for compositions near 60% H2SO4 to 0.146 for compositions near 70% H2SO4. Intermediate conditions gave intermediate results except for low reaction probabilities of about 0.045 at 260 K on aerosols with about 78% H2SO4. The reaction probability did not depend on particle size. These results imply that the reaction occurs essentially at the surface of the particle. A simple model for this type of reaction that reproduces the general trends observed is presented. the presence of formaldehyde did not affect the reaction rate.

Fried, Alan↗

Stratospheric sulfuric acid aerosols: composition and temperature discrimination with the ATMOS data set

The ATMOS Fourier transform spectrometer was flown for a fourth time on the Space Shuttle as part of the ATLAS-3 instrument payload in November 1994. More than 190 sunrise and sunset occultation events provided measurements of more than 30 atmospheric trace gases at latitudes 3-49(deg)N and 65-72(deg)S, including observations both inside and outside the Antarctic polar vortex.

aerosols ATMOS remote sensing↗