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At least 91 records · Page 5

Anthropogenic extremely low volatility organics (ELVOCs) Govern the Growth of Molecular Clusters over the Southern Great Plains during the Springtime

New particle formation (NPF) and growth govern cloud condensation nuclei (CCN) concentrations in many regions. The mechanisms governing the nucleation of molecular clusters vary substantially in different regions of the atmosphere. Additionally, the growth of these clusters from ~2 to 20 nm sizes is often governed by the availability of extremely low volatility organic vapours (ELVOCs). While the pathways to ELVOC formation from the oxidation of biogenic monoterpenes with ozone is better understood, the chemical and mechanistic pathways for ELVOC formation from oxidation of anthropogenic organics are not well understood. We integrate measurements and three-dimensional regional model simulations with the Weather Research and Forecasting Model coupled to chemistry (WRF-Chem) to understand the processes governing new particle formation and growth and secondary organic aerosol (SOA) formation during the Holistic Interactions of Shallow Clouds, Aerosols and Land Ecosystems (HI-SCALE) field campaign at the Southern Great Plains (SGP) observatory in Oklahoma, and contrast it with a site within the Bankhead National Forest (BNF), Alabama in Southeast USA, where 5-year long measurements will begin in 2024. Simulations show that nucleation rates are at least an order of magnitude higher at SGP compared to BNF during the springtime days (April 28 and May 14, 2016), largely due to lower H2SO4 concentrations at BNF, which are needed for nucleation. In addition, the larger CS at BNF (compared to SGP) increase the loss of molecular clusters by coagulation to pre-existing particles. Among the 8 different nucleation mechanisms in WRF-Chem, we find that the amine+H2SO4 nucleation mechanism dominates at the SGP site, while the pure organic ion induced nucleation mechanism dominates over BNF. Through various WRF-Chem sensitivity simulations, we find that anthropogenic ELVOCs are critical for explaining the growth of newly formed particles and the resulting number size distribution observed near the surface at the SGP site during the daytime. In addition, we show that treating organic particles as semisolid, with strong diffusion-limited uptake of organic vapours, brings model predictions into closer agreement with the observed evolution of particle size distribution. Simulations also predict that anthropogenic SOA, formed by the oxidation of aromatic volatile organic compounds (VOCs), is the dominant organic aerosol component at SGP, while biogenic SOA dominates particle composition at the BNF site in Southeast USA on these days.

Shrivastava, ManishKumar B.↗

A Novel Dew Point Meter: Application to the Measurement of the Sulfuric Acid Dew Point for Combustion Flue Gas

Accurate knowledge of acid dew point is essential for industrial and applied combustion. Sulfur in the fuel or raw materials is converted to sulfur dioxide (SO2) during combustion, and a portion of the SO2 is oxidized to sulfur trioxide (SO3). The SO3 will react to form H2SO4 vapor when in the presence of water vapor. Even with just trace levels of H2SO4 vapor in the gas phase (1-10 ppm), the dew point can reach 100°C and higher. To avoid acid condensation and the resulting corrosion on heat recovery equipment, plant engineers must ensure that surface temperatures are above the acid dew point, but this decreases the efficiency of the thermal energy recovery. Thus, there is a trade-off between minimizing equipment corrosion and maximizing thermal energy recovery efficiency, and the acid dew point is a key parameter for this optimization. In this work, we analyze and discuss the theory of the sulfuric acid condensation process and develop a novel dew point meter based on this analysis. The meter consists of a novel optical instrument that is designed to monitor the slightest appearance of condensation on a hydrophobic window surface, and the surface temperature of the window is slowly decreased until condensation is first observed, yielding an accurate measurement of the dew point. The basis of the instrument is that a collimated beam from a diode laser generates scattered light when encountering surface condensate, and a sophisticated array detector is used to sensitively monitor the light scattering. The measurement procedures are established to rapidly find the acid dew point, while minimizing error. Further, we propose a calibration system based on a liquid bubbler, which can generate a stable gas flow with known sulfuric acid dew point, to test the dew point meter. Test results show that the dew point meter can accurately measure the acid dew point over a wide range.

Cheng, Mao↗

Study of the reaction of atomic oxygen with aerosols

The rate of disappearance of atomic oxygen was measured at several pressures in a fast flow pyrex reactor system with its walls treated with (NH4)2SO4 (s), H2SO4 (l), and NH4CL (s). Atomic oxygen, P-3 was generated by dissociation of pure, low pressure oxygen in a microwave discharge. Concentrations of atomic oxygen were measured at several stations in the reactor system using chemiluminescent titration with NO2. Recombination efficiencies calculated from experimentally determined wall recombination rate constants are in good agreement with reported values for clean Pyrex and an H2SO4 coated wall. The recombination efficiency for (NH4)2SO4, results in a slightly lower value than for H2S04. A rapid exothermic reaction between atomic oxygen and the NH4Cl wall coating prevented recombination efficiency determination for this coating. The results show that the technique is highly useful for wall recombination measurements and as a means of extrapolating to the case of free stream aerosol-gas interactions.

Akers, F. I.↗

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.↗

Microwave boundary conditions on the atmosphere and clouds of Venus

The dielectric properties of H2O/H2SO4 mixtures are deduced from the Debye equations and, for a well-mixed atmosphere, the structure of H2O and H2O/H2SO4 clouds is calculated. Various data on the planet together set an upper limit on the mixing ratio by number for H2O of about 0.001 in the lower Venus atmosphere, and for H2SO4 of about 0.00001. The polarization value of the real part of the refractive index of the clouds, the spectroscopic limits on the abundance of water vapor above the clouds, and the microwave data together set corresponding upper limits on H2O of approximately 0.0002 and on H2SO4 of approximately 0.000009. Upper limits on the surface density of total cloud constituents and of cloud liquid water are, respectively, about 0.1 g/sq cm and about 0.01 g/sq cm. The infrared opacities of 90 bars of CO2, together with the derived upper limits to the amounts of water vapor and liquid H2O/H2SO4, may be sufficient to explain the high surface temperatures through the greenhouse effect.

Rossow, W. B.↗

Venus cloud models

Remote observations of Venus are reviewed. The strongest inferences of cloud properties can be drawn from polarization data which provide information about cloud particles near 68 km. Particle properties are not as well determined at higher and lower levels. If the clouds are generated photochemically from reduced sulfur species, the supply of O2 may be an important constraint on cloud production. Vapor-pressure data reviewed, and it is shown that deep clouds cannot be H2SO4-H2O aerosols unless the mixing ratios of both H2SO4 and H2O approach 0.001 below 50 km.

Wofsy, S. C.↗

Determination of carbon by the oxidation reduction reaction with chromium

Free carbon was determined in silicon and boron carbides in ash, oxides, and other materials by oxidation to carbon dioxide with a mixture of K2Cr2O7 + H2SO4. The determination was made from the amount of CR(6) consumed, by adding excess Mohr's salt and titrating with a standard solution of KMnO4. The amount of Cr(6) self reduced was determined in a blank test. Optimum oxidation and conditions were achieved when the volumes of 5% k2Cr2Oz and H2SO4 were equal. The mixture was boiled for 1-2 hours using a reflex condenser. The volume should not be reduced, in order to avoid an increase in the sulfuric acid concentration. The relative error was 4-7% for 0.005-0.04 g C and less than or equal to 3.5% for 0.1 g C.

Mashkovich, L.↗

Properties of the clouds of Venus, as inferred from airborne observations of its near-infrared reflectivity spectrum

The shape and absolute value of Venus' reflectivity spectrum is measured in the 1.2- to 4.0 micrometer spectral region with a circular variable filter wheel spectrometer having a spectral resolution of 1.5%. Comparing these spectra with synthetic spectra generated with a multiple-scattering computer code, a number of properties of the Venus clouds are inferred. Evidence is obtained indicating that the clouds are made of a water solution of sulfuric acid in their top unit optical depth, and that the clouds are made of this material down to an optical depth of at least 25. In addition, the acid concentration is 84 plus or minus 2% H2SO4 by weight in the top unit optical depth, the total optical depth of the clouds is 37.5 plus or minus 12.5, and the cross-sectional weighted mean particle radius lies between 0.5 and 1.4 micrometers in the top unit optical depth of the clouds. It is found that the average volume mixing ratio of H2SO4 and H2O contained in the cloud material both equal approximately 2 x 10 to the -6. Employing vapor pressure arguments, the acid concentration is shown to equal 84 plus or minus 6% at the cloud bottom and the water vapor mixing ratio beneath the clouds lies between 6 x 10 to the -4 and 10 to the -2.

Pollack, J. B.↗

Sulfur dioxide in the Venus atmosphere - Distribution and implications

The Pioneer Venus Orbiter ultraviolet spectrometer sees variable disk brightness features similar to the well-known 'UV markings' seen at longer wavelengths. The bright features are consistent with a homogeneous cloud of H2SO4 aerosols. The darker features show the presence of a broad-band absorber, which is at some depth in the cloud layer. Additional contrast arises from SO2 absorption. The observed strength of the SO2 absorption as a function of wavelength rules out a uniform mixing ratio for the SO2. The data are well fitted by an inhomogeneous light scattering model in which the SO2 scale height is one-fifth of the CO2 scale height, and the mixing ratio of SO2 at 40 mb is 10 to the -7th. A model of the oxidation of sulfur dioxide in the upper cloud reproduces the observed vertical distribution of SO2 and indicates that SO2 alone is sufficient to produce the observed amount of H2SO4 in this region.

Esposito, L. W.↗

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.↗

Ion-induced nucleation in a binary mixture

Recent ion-induced nucleation studies in a binary mixture of H2O and H2SO4 vapors indicate that conventional classical nucleation theories cannot account for the experimentally observed ion-H2O-H2SO4 microcluster spectra. An empirical-analytical, semi-molecular theory of nucleation of a binary mixture of vapors on ions has been developed. This theory includes molecular approach to ion-induced changes in dielectric properties in the immediate neighborhood of an ion core as well as the size dependence of the surface tension of the microcluster. In addition to gaseous sulfuric acid and water molecules, the effect of ion-hydrates and sulfuric acid hydrates has also been considered. This theory is further simplified by using an empirical correction factor for the electrostatic term. This correction factor has been obtained by comparing the simplified model with the molecular dynamics calculations for selected ion hydrate formation. These two theoretical models are then compared with the classical theory for a variety of experimental conditions.

Smith, A. C.↗

The clouds of Venus - Sulfuric acid by the lead chamber process

The Pioneer Venus atmospheric probe provided new data on the clouds of Venus. A model consistent with this data involves SO2 being oxidized to H2SO4 by NO(x) in the presence of H2O. NO(x) also forms nitrosylsulfuric acid (NOHSO4) dissolved in the H2SO4 droplets. This acid solution, along with SO2 and perhaps NO2, can explain the UV and visible reflection spectrum of Venus. In the middle and lower clouds, NOHSO4 forms solid particles.

Sill, G. T.↗

Laboratory evaluation of microwave absorption properties under simulated conditions for planetary atmospheres

The microwave absorbing properties of gaseous sulfuric acid (H2SO4) under Venus atmospheric conditions are investigated. The results are applied to measurements from Mariner 5, Mariner 10, and Pioneer/Venus Radio Occultation experiments, to determine abundancies of gaseous sulfuric acid in the Venus atmosphere. The microwave properties of the vapors accompanying liquid H2SO4 are studied to estimate the vapor pressure in an atmospheric model.

Steffes, P. G.↗

STS 8 Orbiter mission window pitting and the possible association with the El Chichon eruption of March and April 1982

The possibility that the pitting that occurred in the STS-8 Orbiter windows was caused by dust from the El Chichon volcano eruption in March-April 1982 is considered. The pit density was more than 30/sq cm, most being 2.5-5 microns deep, and showed no evidence of impact melting. An 'alley' of higher incidence of pits in one window coincided with the line of a seam between TPS tiles. The particles causing the sandblasting were concluded to have arrived in parallel and could not be attributed to the ET, SRBs or a dust storm. The sulfuric gas-rich El Chichon plume injected sufficient material into the atmosphere so that the globe was soon encircled. Most of the resulting particulates (480-8400 tons) stayed in the Northern Hemisphere, and H2SO4 and ash concentrations were high during the STS-8 mission. The Orbiter cut through the debris layer at 19.8 km altitude at a 10 deg angle of attack, which matches the particle crater impact angle in the Orbiter windows. Since the passage was at night, larger H2SO4 droplets may have coalesced and formed larger particles on available solid nuclei, thus producing the 20-40 microns cratering observed in the windows.

Cour-Palais, B. G.↗

Laboratory measurements of the microwave opacity and vapor pressure of sulfuric acid vapor under simulated conditions for the middle atmosphere of Venus

Microwave absorption measurements at wavelengths of 13.4 and 3.6 cm were made in gaseous H2SO4 in a CO2 atmosphere under simulated conditions for the Venus middle atmosphere. The results suggest that abundances of gaseous H2SO4 on the order of 15-30 ppm could account for the absorption observed by radio occultation measurements at these wavelengths. They also imply that such abundances would correspond to saturation vapor pressure existing at or above the 46-48-km range, which correlates with the observed cloud base.

Steffes, P. G.↗

Evaluation of the microwave spectrum of Venus in the 1.2-22 centimeter wavelength range based on laboratory measurements of constituent gas opacities

Laboratory measurements of the microwave (1.2-22.3 cm) spectrum properties of Venus' gaseous atmospheric constituents were performed using an apparatus for simulating conditions of the middle atmosphere of Venus (gaseous H2SO4 + CO2 at 1 to 6 atm). The results have shown that at wavelengths longer than 1.8 cm, gaseous H2SO4 and CO2 are the predominant microwave absorbers, while at wavelengths from 1.2 to 1.8 cm, SO2 and CO2 are the predominant absorbers. These results were used to develop a model for the microwave emission spectrum of Venus, which correlated well with microwave observations of this planet.

Steffes, Paul G.↗

Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

Rossi, Michel J.↗

The rate of volcanism on Venus

The maintenance of the global H2SO4 clouds on Venus requires volcanism to replenish the atmospheric SO2 which is continually being removed from the atmosphere by reaction with calcium minerals on the surface of Venus. The first laboratory measurements of the rate of one such reaction, between SO2 and calcite (CaCO3) to form anhydrite (CaSO4), are reported. If the rate of this reaction is representative of the SO2 reaction rate at the Venus surface, then we estimate that all SO2 in the Venus atmosphere (and thus the H2SO4 clouds) will be removed in 1.9 million years unless the lost SO2 is replenished by volcanism. The required rate of volcanism ranges from about 0.4 to about 11 cu km of magma erupted per year, depending on the assumed sulfur content of the erupted material. If this material has the same composition as the Venus surface at the Venera 13, 14 and Vega 2 landing sites, then the required rate of volcanism is about 1 cu km per year. This independent geochemically estimated rate can be used to determine if either (or neither) of the two discordant (2 cu km/year vs. 200 to 300 cu km/year) geophysically estimated rates is correct. The geochemically estimated rate also suggests that Venus is less volcanically active than the Earth.

Fegley, Bruce, Jr.↗