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A theory for the time-dependent growth of solution droplets by heteromolecular condensation is presented. The theory is applied to the growth of H2O-H2SO4 aerosols for relative humidities less than 100 per cent. Growth curves (droplet radius as a function of time) for different values of relative humidity are evaluated.
The homogeneous- and heterogeneous-heteromolecular nucleation of H2SO4-H2O solution droplets in the stratosphere is investigated and order-of-magnitude nucleation rates are evaluated. The heterogeneous processes considered are nucleation onto soluble particles, flat insoluble surfaces, spherical insoluble particles, and ions. The relative importance of the various nucleation mechanisms is determined for conditions assumed to correspond to 18 km altitude. Under the assumed conditions, the heterogeneous nucleation rate onto insoluble particles is shown to be about 10 to the 69th times larger than the homogeneous nucleation rate and 10 to the 57th times larger than nucleation onto ions.
Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.
Numerous absoption lines of stratospheric sulfer dioxide (SO2) were identified in solar occulation spectra recorded by the Atmospheric Trace Molecule Spectroscopy (ATMOS) Fourier transform spectrometer during the Atmospheric Laboratory for Applications and Science (ATLAS)-1 shuttle mission (March 24-April 2, 1992). based on their analysis, a volume mixing ratio profile of SO2 increasing from (13 +/- 4) p.p.t.v. (parts per 10(exp -12) by volume) at 16 mbar (approximately 28 km) to 455 +/- 90 p.p.t.v. at 0.63 mbar (approximately 52 km) was measured with no significant profile differences between 20 deg N and 60 deg S latitude. The increase in the SO2 mixing ratios with altitude indicates the presence of a source of SO2 in the upper stratosphere. Profiles retrieved from ATMOS spectra recorded during shuttle flights in April-May 1985 and April 1993 show similar vertical distributions but lower concentrations. Two-dimensional model calculations with SO2 assumed as the end product of H2SO4 photolysis produce SO2 profiles consistent with the ATMOS measuremnts to within about a factor 2.
Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.
Each spring a layer of small particles forms between 20 and 30 km in the polar regions. Results are presented from a 2D microphysical model of sulfate aerosol, which provide the first self-consistent explanation of the observed "CN layer." Photochemical conversion of sulfuric acid to SO2 in the upper stratosphere and mesosphere is necessary for this layer to form. Recent laboratory measurements of H2SO4 and SO3 photolysis rates are consistent with such conversion, though an additional source of SO2 may be required. Nucleation throughout the polar winter extends the top of the aerosol layer to higher altitudes, despite strong downward transport of ambient air. This finding may be important to heterogeneous chemistry at the top of the aerosol layer in polar winter and spring.
This project involves the deployment of a variety of unique aircraft measurements for the PEM-Tropics program. These measurements were all to be accomplished on a near simultaneous basis using a two channel selected ion chemical ionization mass spectrometer instrument. The first year of this project consisted of four components; improve and perform additional testing of the OH, H2SO4, and MSA instrument which had only flown on one previous mission (ACE-I); develop and test the vacuum and electronic hardware and software which would allow two independent mass spectrometer systems to be operated from a single instrument (one vacuum/pumping system); construct an aircraft compatible DMSO/DMS02 ion source and calibration system; and operate the above system on the NASA P-3B during PEM-Tropics. The first two of the components were to be accomplished at NCAR. The third component was to be completed at Georgia Tech and the fourth was to be conducted by researchers from both institutions on the NASA P-3B.
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.
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The quantum yields for producing O2(a (1 delta g)) and O2(b(1 sigma g +)) for the reaction, O + ClO yields Cl + O2, are summarized. Also included are results for other simple reactions capable of producing the singlet oxygen states. An episodic injection of SO2 into the upper atmosphere of Venus is considered as a possible explanation for the airglow values.
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Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.
This project involved the installation of a downsized multichannel mass spectrometer instrument on the NASA P-3B aircraft and its subsequent use on the PEM-Tropics B mission. The new instrument performed well, measuring a number of difficult-to-measure compounds and providing much new photochemical and sulfur data as well as possibly uncovering a new nighttime DMSO source. The details of this effort are discussed.
The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.
Sulfuric acid (H2SO4) is commonly accepted as a key precursor for atmospheric new particle formation (NPF). However, direct measurements of [H2SO4] remain challenging, thus preventing the determination of this important quantity, and, consequently, a complete understanding of its contribution to the NPF process. Several proxies have been developed to bridge the gaps, but their ability to predict [H2SO4] in very specific conditions such as those encountered in volcanic plumes (including in particular high sulphur dioxide mixing ratios) has not been evaluated so far. In this context, the main objective of the present study was to develop new proxies for daytime [H2SO4] in volcanic plume conditions and compare their performance to that of the proxies available in the literature. In specific, the data collected at Maïdo during the OCTAVE 2018 campaign, in the volcanic eruption plume of the Piton de la Fournaise, were first used to derive seven proxies based on the knowledge of sulphur dioxide (SO2) mixing ratio, global radiation, condensation sink (CS) and relative humidity (RH). In three of the seven proxies (F1–F3), all variables were given equal weight in the prediction of [H2SO4], while adjusted powers were allowed for the different variables in the other four proxies (A1–A4). Proxies A1–A4 were overall found to perform better compared to F1–F3, with, in specific, improved predictive ability for [H2SO4] > 2 × 108 per cu.cm. The CS was observed to play an important role in regulating [H2SO4], while, in contrast, the inclusion of RH did not improve the predictions. A last expression accounting for an additional sink term related to cluster formation, S1, was also tested and showed a very good predictive ability over the whole range of measured [H2SO4]. The newly developed proxies were in a second step further evaluated using airborne measurements performed in the passive degassing plume of Etna during the STRAP 2016 campaign. Increased correlations between observed and predicted [H2SO4] were obtained when the dependence of predicted [H2SO4] over CS was the lowest, and when the dependence over [SO2] was concurrently the highest. The best predictions were finally retrieved by the simple formulation of F2 (in which [SO2] and radiation alone were assumed to explain the variations of [H2SO4] with equal contributions), with a pre factor adapted to the STRAP data. All in all, our results illustrate the fairly good capacity of the proxy available in the literature to describe [H2SO4] in volcanic plume conditions, but highlight at the same time the benefit of the newly developed proxies for the prediction of the highest concentrations ([H2SO4] > 2–3 × 108 per cu.cm). Also, the contrasting behaviours of the new proxies in the two investigated datasets indicate that in volcanic plumes like in other environments, the relevance of a proxy can be affected by changes in environmental conditions, and that location specific coefficients do logically improve the predictions.
During the course of this project, we performed exhaustive research and development of SO3/H2SO4 sensing technology for coal-fired power plant applications (Figure 1). The development culminated in a successful field campaign of a prototype continuous real-time H2SO4 monitor at a coal-fired power plant (TRL 6) accomplishing the primary goal of the project. The developed sensors utilize tunable laser absorption spectroscopy (TLAS) operating in the mid-infrared (Mid-IR) wavelength region, which is the so-called “molecular fingerprint” region. Systems operating in the Mid-IR have orders of magnitude more sensitivity than systems operating at shorter wavelengths, such as near-infrared (NIR). However, NIR systems are more widespread due to more mature supporting technology (e.g., fiber optics, optical components, etc.). In this project, we not only produced a specific Mid-IR sensor, we also advanced Mid-IR sensor technology in general through the development and demonstration of such supporting technology. In this project, we also developed proprietary broad tuning lasers enabling the ability to effectively measure SO3, H2SO4, H2O, and SO2. Different molecular species have unique spectral signatures that can be probed with lasers operating at different wavelengths. Standard TLAS uses relatively narrow wavelength tuning distributed feedback (DFB) lasers, which can typically only target a single species with narrow features, and are not appropriate for species with broad features, such as SO3 or H2SO4. In contrast, by developing unique, broad-tuning laser technology, we were able to measure these species, as well as SO2 and H2O simultaneously. Furthermore, to enable real-time analysis at a power plant, we modified a commercially available heated gas cell to operate in the Mid-IR wavelength range and fiber coupled the lasers to enable remote delivery of the beams. To generate reference data (library spectra), our collaborators at the University of California Irvine (UCI) developed a catalytic SO3 generation facility. It is worth mentioning that representative H2SO4 and SO3 Mid-IR spectra are not a part of any publicly available database and the data generated under this project is a valuable resource in and of itself. In addition, based on the UCI study we determined that detection of SO3 is complicated by the very strong SO2 absorption. For that reason, we concentrated on H2SO4 detection. Since SO3 and H2SO4 exist in a flue gas in a state of equilibrium, which depends on temperature and humidity, by measuring water concentration and controlling the temperature of the gas cell, we developed an approach to determine SO3 concentration from the H2SO4 measurement. During the development phase of the project, we performed three testing campaigns at our collaborator’s FERCo flue gas facility with conditions representative of the coal-fired power plant (~ 40ppm SO3, 1700ppm to 2800 ppm SO2, 10% water) with the exception of particulate matter. After three test campaigns at FERCo we performed field testing at Harrison Power Station. The final system was mounted on a duct and measured H2SO4, SO2 and water. The tests were highly successful with a demonstrated real-time H2SO4 precision of 1 ppm with a 1 second update. Our collaborators at EPRI conducted an industry survey and determined that there is a very high interest for the SO3/H2SO4 monitoring in the power generation industry as well as in heavy industries in general. Furthermore, work performed by OptoKnowledge beyond the scope of this project under a synergistic DOE SBIR determined another approach to SO3 detection. We applied for Phase II on this SBIR for development a of versatile SO3/H2SO4 sensor but were not selected. We are currently looking for another opportunity to leverage all the technological advancements produced by this project including but not limited to the flue gas facility at UCI, the hardware and software developed, and relationships with FERCo, EPRI CEMTEK, and Harrison Station.
We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.