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At least 163 records · Page 9

Analysis of spectrophotometric observations of Venus in the 3-4 micron region

Spectrophotometric data of Venus in the 3-4 micron region are analyzed in the context of current ideas concerning cloud properties. The results show that a homogeneous cloud model, using a unimodal particle size distribution compatible with the results of previous polarization studies, cannot satisfactorily explain the infrared observations. Assuming a composition of 75% H2SO4, agreement is possible if an upper layer of smaller particles is added to the homogeneous cloud. This inhomogeneous cloud structure, however, is not in agreement with the polarization results. Other models, involving bimodal particle size distributions, were also unsuccessful in explaining both sets of observations in a consistent manner.

Martonchik, J. V.↗

A global average model of atmospheric aerosols for radiative transfer calculations

A global average model is proposed for the size distribution, chemical composition, and optical thickness of stratospheric and tropospheric aerosols. This aerosol model is designed to specify the input parameters to global average radiative transfer calculations which assume the atmosphere is horizontally homogeneous. The model subdivides the atmosphere at multiples of 3 km, where the surface layer extends from the ground to 3 km, the upper troposphere from 3 to 12 km, and the stratosphere from 12 to 45 km. A list of assumptions made in construction of the model is presented and discussed along with major model uncertainties. The stratospheric aerosol is modeled as a liquid mixture of 75% H2SO4 and 25% H2O, while the tropospheric aerosol consists of 60% sulfate and 40% soil particles above 3 km and of 50% sulfate, 35% soil particles, and 15% sea salt below 3 km. Implications and consistency of the model are discussed.

Toon, O. B.↗

A kinetic study of the interaction between atomic oxygen and aerosols

This study was concerned with the effects of NH4Cl and (NH4)2SO4 aerosols on the kinetics of disappearance of atomic oxygen. Atomic oxygen was generated by a 2.45-GHz microwave discharge and the kinetics of disappearance measured in a fast flow system using NO2 titration. Values of the recombination coefficient for heterogeneous wall recombination were determined for clean, H2SO4-coated, and (NH4)2SO4-coated Pyrex to be 0.000050, 0.000020, and 0.000019, respectively. A rapid exothermic chemical reaction was found to occur between atomic oxygen and an NH4Cl wall coating; the products were NH3, NO, H2O, and HCl. The NH4Cl aerosol was generated by gas phase reaction of NH3 with HCl. The aerosol particles were approximately spherical and nearly monodisperse with a mean diameter of 1.6 plus or minus 0.2 micron. The rate constant for the disappearance of atomic oxygen in the presence of NH4Cl aerosol was measured. No significant decrease was observed in the rate of disappearance of atomic oxygen in the presence of an (NH4)2SO4 aerosol at a concentration of 285 mg per cu m.

Akers, F. I.↗

Stratospheric aerosols and climatic change

Generated primarily by volcanic explosions, a layer of submicron silicate particles and particles made of concentrated sulfuric acids solution is present in the stratosphere. Flights through the stratosphere may be a future source of stratospheric aerosols, since the effluent from supersonic transports contains sulfurous gases (which will be converted to H2SO4) while the exhaust from Space Shuttles contains tiny aluminum oxide particles. Global heat balance calculations have shown that the stratospheric aerosols have made important contributions to some climatic changes. In the present paper, accurate radiative transfer calculations of the globally-averaged surface temperature (T) are carried out to estimate the sensitivity of the climate to changes in the number of stratospheric aerosols. The results obtained for a specified model atmosphere, including a vertical profile of the aerosols, indicate that the climate is unlikely to be affected by supersonic transports and Space Shuttles, during the next decades.

Baldwin, B.↗

Physical-chemical examination of the N2O3-SO3-H2O system

It was found that when (NO)HSO4 is added to absolute H2SO4, specific conductivity rises sharply, possibly due to an increase in mutual interionic effects and viscosity as the (NO)HSO4 concentration rises. The addition of SO3 to the solution yielded a precipitate; a combination of analysis, IR spectroscopy and X-ray diffraction techniques indicated that this precipitate was (NO)HS2O7.

Linstroem, C.↗

Albedo enhancement and perturbation of radiation balance due to stratospheric aerosols

The effect of stratospheric aerosols on the earth's monthly zonal radiation balance is investigated using a model layer consisting of 75% H2SO4, which is the primary constituent of the background aerosol layer. The reduction in solar energy absorbed by the earth-atmosphere system is determined through the albedo sensitivity, defined here as the change in albedo per unit mid-visible optical depth of the aerosol layer. The optically thin approximation is used in conjunction with the Henyey-Greenstein phase function for scattering to simplify computations. Satellite derived planetary albedos are used as the frame of reference about which the change in albedo is computed. An infrared radiative transfer model is used to estimate the increased greenhouse effect attributed to the aerosol layer. The infrared heating tends to compensate for the albedo effect in altering the radiation balance. The results indicate that the dominant influence of the thin model stratospheric aerosol layer is an increased reflection of solar energy all over the globe except for the polar-winter region, but the change in the radiation balance is seen to be uniform and small equatorwards of 50%.

HARSHVARDHAN↗

The effects of cations and anions on hydrogen chemisorption at Pt

Experimental evidence based on linear sweep voltammetry is presented to substantiate the view that ionic adsorption substantially shifts electrode potentials in addition to the relative heights of the hydrogen adsorption peaks. HClO4 and HF are chosen as better reference electrolytes for anion studies. The voltammetry curves for 0.1M HF and 0.1M HClO4 as well as the effect of adding successively increasing amounts of H2SO4 to these electrolytes are discussed. The measurements are also extended to alkaline solutions. Mechanisms whereby the addition of various cations and anions to electrolytes such as HF and HClO4 can induce changes in the structure of the hydrogen adsorption region in the voltammetry curves are identified: (1) blocking of sites by anion adsorption and coupling of hydrogen adsorption and anion desorption, (2) modification in the hydrogen adsorption energies for sites adjacent to adsorbed anions, (3) changes in the potential distribution across the interface, and (4) surface restructuring.

Huang, J. C.↗

Nitrogen-sulfur compounds in stratospheric aerosols

Two forms of nitrosyl sulfuric acid (NOHSO4 and NOHS2O7) have been tentatively identified in stratospheric aerosols. The first of these can be formed either directly from gas reactions of NO2 with SO2 or by gas-particle interactions between NO2 and H2SO4. The second product may form when SO3 is involved. Estimates based on these reactions suggest that the maximum quantity of NO that might be absorbed in stratospheric aerosols could vary from one-third to twice the amount of NO in the surrounding air. If these reactions occur in the stratosphere, then a mechanism exists for removing nitrogen oxides from that region by aerosol particle fallout. This process may typify another natural means that helps cleanse the lower stratosphere of excessive pollutants.

Farlow, N. H.↗

Chemistry and thermodynamics of sulfur on Venus

Sulfur reactions on Venus are discussed. It is suggested that photochemical reactions convert SO2 to H2SO4 and remove O2 from the Venus stratosphere, while thermochemical reactions near the surface probably make the SO2, regenerate CO2 from photolytic CO, and produce free sulfur. Optical evidence for liquid sulfur on Venus is examined; the Venera data suggest a light drizzle of liquid sulfur above 18 km and the existence of several per cent of sulfur vapor below that height.

Young, A. T.↗

Simulated lidar return from a one-dimensional stratospheric aerosol model

Results are presented for theoretical calculations of lidar backscatter at wavelengths of 0.6943 and 1.06 microns from the stratospheric aerosol. The computations are based on the size distribution, particle number density, and particle composition predicted by a one-dimensional model of the stratospheric aerosol layer that assumes that the primary source of sulfur to the stratosphere is biogenic OCS released at ground level. The aerosol particles are taken to be spherical liquid H2SO4-H2O solution droplets with solid cores, which undergo condensation, evaporation, coagulation, sedimentation, and vertical eddy mixing. The theoretical backscatter profiles are compared with experimental results obtained from actual lidar observations of the stratospheric aerosol layer before and after the eruption of Volcan de Fuego in October 1974. The model predictions are shown to be in good agreement with the average of a number of observations.

Hamill, P.↗

The 12- to 20-micron spectrum of Venus - Implications for temperature and cloud structure

The spectrum of Venus was measured between approximately 500 and 800 kaysers (12 to 20 microns) at a resolution of 3.12 kaysers from the NASA C141 G. P. Kuiper Airborne Observatory on 22 and 24 February 1977. The spectrum clearly shows the detailed structure of CO2 absorption in the vicinity of the nu-2 fundamental band at 667 kaysers. In addition, details of model fitting demonstrate the possibility for a cold and thin haze of sulfuric acid droplets along with an optically opaque cloud top near 250 K. Such clouds represent major differences from other H2SO4 main cloud deck models in the recent literature and may be indicative of changes in the vertical distribution of aerosols on a global scale. The temperatures retrieved for pressures at or below 10 mbar are largely independent of the cloud model assumed and they are some 16 to 20 K warmer than the 1972 NASA model. All retrieved temperatures lie within the range of Mariner 5 and Mariner 10 radio occultation inversion results.

Aumann, H. H.↗

Perturbation of the zonal radiation balance by a stratospheric aerosol layer

The effect of stratospheric aerosols on the earth's monthly zonal radiation balance is investigated using a model layer consisting of 75% H2SO4, the primary constituent of the background aerosol layer. The reduction in solar energy absorbed by the earth-atmosphere system is determined through the albedo sensitivity, and the optically thin approximation is used in conjunction with the Henyey-Greenstein phase function for scattering. An infrared radiative transfer model is used to estimate the increased greenhouse effect from the aerosol layer, and the infrared heating compensates for the albedo effect in altering the radiation balance. The results indicate that the dominant influence of the thin model stratospheric aerosol layer is an increased reflection of solar energy all over the globe except for the polar-winter region, but the change in the radiation balance is uniform and small equatorward of 50 deg.

Harshvardhan, MR.↗

Boundary layer measurements of the OH radical in the vicinity of an isolated power plant plume - SO2 and NO2 chemical conversion times

Direct measurements of the OH radical in the vicinity of an isolated power plant plume are reported. These measurements were used to estimate the conversion time of SO2 to H2SO4-sulfate aerosol via the initiating step OH + SO2 + M yields HSO3. Using the near-high-noon measured value of OH (9.5 million per cu cm), resulted in a 1/e conversion time of 1.4 days. The latter lifetime would correspond to a conversion rate of about 2%/hr. When the lifetime calculation was modified to take into consideration the OH diurnal cycle, the 1/e conversion time for SO2 was found to be 4.4 days, giving an apparent overall rate of conversion of about 0.7%/hr. Similar calculations carried out for the conversion of NO2 to NHO3 resulted in 1/e lifetimes for NO2 of 2-3 h for midday time periods.

Davis, D. D.↗

The enhanced oxidation of SO2 by NO2 on carbon particulates

The oxidation of SO2 on carbon particles in dry air and in air at 65% relative humidity (RH) was found to be greatly enhanced by the presence of gaseous NO2. Exposures of 20-80ppm SO2 + 10ppm NO2 on 1-mg samples of commercial carbon black were found to produce both sorption and desorption coverages (weight retained after desorption into N2) of over one order of magnitude greater than for corresponding SO2 exposures. Significant agglomeration and wetting were observed to occur progressively during exposures at 65% RH, and samples, even after 150-h exposure, rarely reached steady-state weight gain. The wetting may have regenerated fresh reactive carbon surface. Sorptions conducted in nitrogen atmospheres, rather than in air, appeared to produce slightly higher sorptions and weight retentions for equivalent exposure concentrations and times, indicating that NO2 served as the oxidizer and that molecular oxygen, or some trace constitutents in air, may have weakly inhibited the oxidation by NO2. Wet chemical analysis of the desorbed phase indicated that sulfate, presumably H2SO4 accounted for over half of the retained weight. Measurements of pH from water-quenched samples indicated a highly acidic surface phase, and suggested the oxidation process could proceed in an acidic environment.

Cofer, W. R., III↗

Evolution of the atmosphere of Venus

The photochemistry of the stratosphere of Venus was modeled using an updated and expanded chemical scheme, and the results of recent laboratory studies. The model satisfactorily accounts for the observations of CO, O2, (1) and SO2 in the stratosphere. Oxygen, derived from CO2 photolysis, is primarily consumed by CO2 recombination and oxidation of SO2 to H2SO4. Photolysis of HCl in the upper stratosphere provides a major source of odd hydrogen radicals essential for the catalytic oxidation of CO. Oxidation of SO2 by O occurs in the lower stratosphere, with the O-O bond broken by S + O2 and SO + HO2. The sensitivity of stratospheric chemistry to ambient H2 abundance was studied and the model prefers the high value (1 10 ppm) recently inferred from the Pioneer Venus ionospheric measurements. The importance of the photochemical production of S2O, (SO)2, S2, H2S2O2 and H2S2O3 is speculated. A number of previously unsuspected similarities between the chemistry of the stratospheres of Venus and the Earth, presented and discussed.

Yung, Y. L.↗

Effects of meteoric debris on stratospheric aerosols and gases

Characterizations of meteoric dust height and size distributions are obtained using Hunten's calculations of meteor ablation and recondensation rates. The contribution of meteor residues to aerosol composition, the role of meteoric dust as condensation nuclei, and the effects of meteor debris on aerosol size distributions are quantified, and particle surface areas are estimated. The potential importance of heterogeneous chemistry for stratospheric trace gases is discussed. The interaction between H2SO4 vapor and meteor metal vapors is investigated. It is concluded that meteoric particles may dominate the natural stratospheric aerosols at small (less than .01 micron radius) and large (greater than 1 micron radius) sizes under normal conditions.

Turco, R. P.↗

Photochemistry of SO2 in Venus' upper cloud layers

The photochemical and transport processes that occur in the Venusian atmosphere in and above the upper cloud region are characterized with attention to the correlation with the Pioneer Venus spectrometer results for the cloud top SO2 distribution. The model uses upward-flowing SO2 and H2O to replace the sulfur and hydrogen lost through the lower boundary by the settling of sulfuric acid aerosols. Oxygen for the oxidation of SO2 to SO3 prior to hydration to H2SO4 is supplied by the photolysis of CO2. A model with SO2 as the major sulfur-bearing gas is consistent with the Pioneer data.

Winick, J. R.↗