Interactions of Sulfur Dioxide with Insoluble Suspended Particulate Matter

A laboratory study was conducted of the heterogeneous catalysis of sulfur dioxide at ppm concentrations in air by insoluble particles of CaCO₂, V₂O₅, Fe₂0₃, flyash from a coal-burning power plant, MnCO₂, activated carbon, and suspended particulate matter from urban air. The investigalion was performed by utilizing a new technique for aerosol stabilization which consists of depositing the aerosol on Teflon beads in a fluidized bed. The Teflon beads with deposited aerosol particles were then packed into a flow reactor. Progress of the chemical reaction of SO₂ with deposited particles was continuously monitored by determining the SO₂ concentrations in the reactor effluent with a microcoulometer.

In this investigation, CaCOg, V₂O₅, and flyash were essentially inert to SO₂ at room temperature. Fe₂O₃, activated carbon, MnO₂, and suspended particulate matter from urban air sorbed SO₂ from air streams with up to 14.4 ppm SO₂ in air. Evidence is presented which suggests that a substantial part of the sorbed SO₂ was physically adsorbed.

Bioassay procedures which utilize pulmonary flow resistance changes in guinea pigs to monitor response to inhaled SO₂-aerosol mixtures in air have indicated the weak or non-potentiating capacity of insoluble aerosols as contrasted to soluble aerosols. Potentiating response of an aerosol appears to be strongly associated with reaction of SO₂ in a water droplet containing aerosol ions and not with physically adsorbed SO₂ on an insoluble aerosol.     

Chain Scission of Polymers by Small Concentrations (1 to 5 ppm) of Sulfur Dioxide and Nitrogen Dioxide,Respectively, in Presence of Air and Near Ultraviolet Radiation

Results are presented as to the extent of chain scission (crosslinking) suffered by various polymers exposed to 1 atm of air and near ultraviolet light (λ > 2800 Å) in presence and absence of nitrogen dioxide, sulfur dioxide, and ozone, respectively, in the concentration range of 1 to 5 ppm. Vinyl polymers are scarcely affected by SO₂ and NO₂, respectively; however, nylon and elastomers are quite sensitive toward these gases. These conclusions agree with observations, found in the literature, on tensile tests, elongations, flexibilities, and infrared measurements in presence of sulfur dioxide under similar conditions.     

The Survival of Airborne Serratia marcescens in Urban Concentrations of Sulfur Dioxide

Aerosols of Serratia marcescens ATCC 274 were suspended in a 709L rotating drum at 20 ± 1 °C and high to mid-range relative humidities. At specified times after bacterial aerosolization, sulfur dioxide was added to concentrations of 2.5, or 5 mg/m³. Viable cell decay rate constants, in control aerosols without added sulfur dioxide, increased rapidly from near 100% to 60% RH in the first hour (termed: young aerosol) of suspension, and from a minimum rate constant at 80% in the succeeding four hours (termed: old aerosol).Upon addition of sulfur dioxide to a cloud of S. marcescens, generally, viable cell decay rate constants increased further. One exception was at 80% relative humidity where maximum resistance to SO₂ accelerated death was observed for old aerosols. Cells in young aerosols were particularly sensitive to SO₂ addition at mid-range humidities, while in older aerosols the cells were insensitive to up to 5 mg SO₂/m³ introduced at high RH; but were up to 10 times more sensitive than cells in young aerosols to a given increase (from 2.5 to 5 mg/m³) in SO₂ concentration at mid-range humidities.     

Present and potential future contributions of sulfate,black and organic carbon aerosols from China to global air quality,premature mortality and radiative forcing

Aerosols are harmful to human health and have both direct and indirect effects on climate. China is a major contributor to global emissions of sulfur dioxide (SO₂), a sulfate (SO₄^2?) precursor, organic carbon (OC), and black carbon (BC) aerosols. Although increasingly examined, the effect of present and potential future levels of these emissions on global premature mortality and climate change has not been well quantified. Through both direct radiative effects and indirect effects on clouds, SO₄^2? and OC exert negative radiative forcing (cooling) while BC exerts positive forcing (warming). We analyze the effect of China's emissions of SO₂, SO₄^2?, OC and BC in 2000 and for three emission scenarios in 2030 on global surface aerosol concentrations, premature mortality, and radiative forcing (RF). Using global models of chemical transport (MOZART-2) and radiative transfer (GFDL RTM), and combining simulation results with gridded population data, mortality rates, and concentration–response relationships from the epidemiological literature, we estimate the contribution of Chinese aerosols to global annual premature mortality and to RF in 2000 and 2030. In 2000, we estimate these aerosols cause approximately 470 000 premature deaths in China and an additional 30 000 deaths globally. In 2030, aggressive emission controls lead to a 50% reduction in premature deaths from the 2000 level to 240 000 in China and 10 000 elsewhere, while under a high emissions scenario premature deaths increase 50% from the 2000 level to 720 000 in China and to 40 000 elsewhere. Because the negative RF from SO₄^2? and OC is larger than the positive forcing from BC, Chinese aerosols lead to global net direct RF of ?74 mW m^?2 in 2000 and between ?15 and ?97 mW m^?2 in 2030 depending on the emissions scenario. Our analysis indicates that increased effort to reduce greenhouse gases is essential to address climate change as China's anticipated reduction of aerosols will result in the loss of net negative radiative forcing.     

Inhalation Route Effects on Exposure to 2.0 Parts Per Million Sulfur Dioxide in Normal Subjects

A number of Investigations have attributed the control of the nasal to oral/nasal ventilation transition to nasal resistance. To investigate possible changes In nasal resistance due to sulfur dioxide (SO₂) exposure, 14 subjects (7 men and 7 women), healthy nonsmokers, between the ages of 20 and 46 years, were exposed for 30 minutes to filtered air while free breathing and to 2.0 ppm SO₂ with either free breathing, forced oral or forced nasal breathing with continuous exercise at a workload 300 kg>m/min below the workload which Initiated cross-over from nasal to oral/nasal breathing in a preliminary incremental workload test. An Incremental work test under the ambient conditions was performed immediately following the 30-minute exercise to ascertain any change in the cross-over ventilation. Pre- and post-measures of pulmonary functions were obtained to ascertain any changes In these parameters due to the exposure. There was a significant difference in the workload at which cross-over occurred following forced oral breathing in 2.0 ppm sulfur dioxide. The nasal ventilation prior to cross-over and the nasal component of ventilation were significantly smaller for this exposure condition, indicating a possible change in nasal dynamics following the 30 minutes of forced oral breathing in 2.0 ppm SO₂. Lack of concomitant changes in pulmonary function tests including airway resistance suggests that breathing 2.0 ppm SO₂ does not affect normal subjects whether administration is by free, forced oral or forced nasal breathing.     

Determination of Sulfur Oxides in the Flue Gases of the Pulping Processes

The body of information presented in this paper is directed to the operating personnel and process engineers employed in the power and recovery departments of a chemical pulping operation. The proper evaluation of the total analytical and sampling system (TASS), to be used in the determination of sulfur oxides is as important as a proper analytical and recording system (ARS). The presence of other sulfur gaseous compounds and particulates could greatly influence the results of the determination.

The analytical method employed determines sulfur dioxide and trioxide from an aliquot of the trapping solution, 3% hydrogen peroxide and 8 0% isopropyl alcohol respectively. The aliquot is titrated with barium perchlorate in the presence of Thorin indicator. The results of evaluating the method indicated negligible interference from the presence of hydrogen sulfide, mercaptans and nitrogen oxides. A blank correction of 15 parts per million (ppm) is recommended whenever 100 ppm of hydrogen sulfide or more are simultaneously present in the gas stream. Particulaies are shown to interfere either by addition or subtraction. Sulfate particulates that will add to the determination must be removed, but in doing so, care must be exerted to avoid surface-contacting conditions that promote reaction between carbonates and the sulfur oxides. The integrated method of sampling and analysis will permit determinations from a flue gas with sulfur oxides concentrations of 30 ppm and above. The relative standard deviation improves from 10% at 100 ppm SO₂ to 2.6% at 1000 ppm SO₂. In both cases, sulfides were present.     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Public Relations Handbook

A major difficulty encountered in laboratory research on the atmospheric interaction of an aerosol-gas system is the unstable nature of the aerosol phase. Previously reported aerosol stabilizing techniques often severely alter the aerosol so that laboratory results cannot be validly extrapolated to the atmospheric environment. A new technique which does not alter the nature of the aerosol is described in this paper.

Aerosol particles are deposited on an inert substrate such as Teflon beads. The deposition is carried out in a fluidized-bed to ensure discrete aerosol deposition and to achieve a uniform distribution of aerosol concentration on the supporting beads. Aerosol-gas interactions can be investigated conveniently by exposing these stabilized aerosols to the reacting gases in dynamic or static systems. Laboratory results obtained by using stabilized aerosols may be extrapolated to the atmospheric environment.

This aerosol stabilizing technique was incorporated into an investigation of the particulate-catalyzed atmospheric oxidation of sulfur dioxide. Teflon beads with deposited aerosol particles of CuCl₂, MnCl₂, and NaCI were exposed to 4–42 ppm of sulfur dioxide in a plug flow reactor. The rate of oxidation of sulfur dioxide was found to be influenced by type of catalyst, concentration of catalyst, relative humidity and concentration of sulfur dioxide. The rate of oxidation by sodium chloride particulate was measurable at low to moderate relative humidities (45–60%), but the rate was several times higher when the sodium chloride catalyst particles change from solid form into droplet form at high relative humidities (>80%).     

High Volume Sampling of Acid Mist

Many nonferrous metals are produced from sulfur-bearing minerals. When pyrometallurgical processes are used, sulfur dioxide gas is formed as a byproduct. In many cases, a small but significant portion of the SO₂ is oxidized further to SO₃ within the pyrometallurgical reactor system. Upon cooling of the gases, as would occur when such gases contact the atmosphere, SO₃ will absorb moisture and condense as a sulfuric acid aerosol, typically referred to as acid mist.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

Biochemical and Physiological Detection of Sulfur Dioxide Injury to Pea Plants (Pisum sativum)

Biochemical and physiological experiments were conducted on pea plants (Pisum sativum) continuously exposed in growth chambers to SO₂ gas for 18 days. S0₂ gas concentrations were 0.1, 0.15, and 0.25 ppm. In plants exposed to 0.1 and 0.15 ppm it was clearly demonstrated that there was a greater accumulation of inorganic sulfur, a reduced buffer capacity of the cells relative to H-ions, and a stimulation of glutamate dehydrogenase activity. The only macroscopic symptom seen was slight chlorosis of the older leaves. There was only a slight decrease in fresh and dry weights of these plants compared to the control plants whereas in the group of plants exposed to 0.25 ppm SO₂ foliage necrosis was considerable. In addition, there was a marked reduction in the fresh and dry weights of the latter plants. However, the relationship among accumulated inorganic sulfur, reduced buffer capacity, and increased glutamate dehydrogenase activity as seen for the lower S0₂ concentrations was close. Accordingly, if might be possible to use these three parameters to diagnose S0₂ injury before any significant symptoms appear. In the case of severe SO₂ injury there was a marked increase in glutamine and ammonia concentrations suggesting that these factors in addition to the above could be used in diagnosing severe SO₂ injury. There was no significant difference between plants treated with 0.1 or 0.15 ppm SO₂ and control plants in the contents of K, Ca, P, and N fractions. Therefore, these factors would not be useful in the early detection of SO₂ injury.     

Shock Wave Cleaning of Air Filters

The trends in and relationships between ambient air concentrations of sulfur dioxide and sulfate aerosols at 48 urban sites and 27 nonurban sites throughout the U.S. between 1963 and 1972 have been analyzed. The substantial decreases in ambient SO₂ concentrations measured at urban sites in the eastern and midwestern U.S. are consistent with the corresponding reductions in local SO₂ emissions, but these decreases have been accompanied by only modest decreases in ambient sulfate concentrations. Large differences in the amounts of SO₂ emitted within individual air quality control regions are associated with much smaller differences in the corresponding ambient sulfate concentrations. Substantial changes in the patterns of SO₂ emissions between air quality regions result in essentially no differences between ambient sulfate concentrations in those air quality regions. Comparisons of several air quality regions in the eastern and western U.S. with similar SO₂ emission levels and patterns of emissions clearly demonstrates the higher ambient sulfate concentration levels in eastern air quality control regions. Relationships between SO₂, sulfates, and vanadium concentrations at eastern nonurban U.S. sites cannot be explained by local emission sources. These various observed results can be best explained by long distance sulfur oxide transport with chemical conversion of SO₂ to sulfates occurring over ranges of hundreds of kilometers. This conclusion has been suggested earlier and the present analysis strongly supports previous discussions. An impact of long range transport of sulfates is to emphasize the need for Consistent strategies for reduction of sulfur oxides throughout large geographical regions. Additions of large capacities involving elevated sources in mid-continental or western regions could result in significant increases in sulfate concentrations well downwind of such sources. Some of the types of research activities required to quantitate crucial experimental parameters are discussed.     

Sulfur processing in the marine atmospheric boundary layer: A review and critical assessment of modeling uncertainties

Sulfur is an extremely motile and vital element in the Earth's biogeochemical environment, one whose active redox chemistry maintains small reservoirs in the atmosphere and biosphere yet large fluxes through both. Essential for life, intimately linked to the climate state, and an important component of air quality, sulfur and its transport and processing in the atmosphere have been the subject of active research for several decades. This review article describes the current state of our understanding of the atmospheric sulfur cycle, focusing on the marine atmospheric boundary layer, with the aim of identifying the largest roots of uncertainty that most inhibit accurate simulation of sulfur cycling in the atmosphere. An overview of the emissions by phytoplankton and shipping, dispersion and entrainment in the marine boundary layer, and chemical processing by aerosols, clouds, and dry deposition is presented. Analysis of 20 contemporary modeling studies suggests that the greatest ambiguity in global sulfur cycling derives from (in descending order) wet deposition of aerosol sulfate, dry deposition of sulfur dioxide to the Earth's surface, and the heterogeneous oxidation of SO₂ in aerosols and clouds.     

Analysis of air quality in Dire Dawa,Ethiopia

Ambient air quality was monitored and analyzed to develop air quality index and its implications for livability and climate change in Dire Dawa, Ethiopia. Using survey research design, 16 georeferenced locations, representing different land uses, were randomly selected and assessed for sulfur dioxide (SO₂), nitrogen dioxide (NO₂), carbon dioxide (CO₂), carbon monoxide (CO),volatile organic compounds (VOCs), and meteorological parameters (temperature and relative humidity). The study found mean concentrations across all land uses for SO₂ of 0.37 ± 0.08 ppm, NO₂ of 0.13 ± 0.17 ppm, CO₂ of 465.65 ± 28.63 ppm, CO of 3.35 ± 2.04 ppm, and VOCs of 1850.67 ± 402 ppm. An air quality index indicated that ambient air quality for SO₂ was very poor, NO₂ ranged from moderate to very poor, whereas CO rating was moderate. Significant positive correlations existed between temperature and NO₂, CO₂, and CO and between humidity and VOCs. Significant relationships were also recorded between CO₂ and NO₂ and between CO and CO₂. Poor urban planning, inadequate pollution control measure, and weak capacity to monitor air quality have implications for energy usage, air quality, and local meteorological parameters, with subsequent feedback into global climate change. Implementation of programs to monitor and control emissions in order to reduce air pollution will provide health, economic, and environmental benefits to the city.

Implications: The need to develop and implement emission control programs to reduce air pollution in Dire Dawa City is urgent. This will provide enormous economic, health, and environmental benefits. It is expected that economic effects of air quality improvement will offset the expenditures for pollution control. Also, strategies that focus on air quality and climate change present a unique opportunity to engage different stakeholders in providing inclusive and sustainable development agenda for Dire Dawa.     

On the oxidation of SO2 to sulfate in atmospheric aerosols

This paper presents the results of a study to investigate the atmospheric oxidation of sulfur dioxide (SO₂). A detailed model of gas-phase chemistry, aerosol thermodynamics and aerosol chemistry is employed to simulate atmospheric sulfate formation. The calculations indicate that, in addition to the gasphase oxidation by hydroxyl (OH) radicals, SO₂ oxidation in aqueous aerosols may also contribute significantly to sulfate formation. Reactions of SO₂ with hydrogen peroxide (H₂O₂) and O₂ (catalyzed by Fe³⁺ and Mn²⁺) are identified as principal aqueous-phase oxidation mechanisms. The results of this study confirm the conclusions drawn from the analysis of ambient aerosol data qualitatively. However, some discrepancies also exist between the results of our modeling study and field data. Such discrepancies emphasize the need for the collection of ambient data for a more rigorous and quantitative evaluation of atmospheric aerosol models.     

Further Effects of Temperature and Pressure on Photochemical Oxidant Production

A procedure is described for producing a sulfur dioxide (SO₂) contaminated atmosphere within a body plethysmograph, exposing man to this atmosphere while maintaining the SO₂ concentration at a given level, and measuring the concentration with less than a oneminute lag time. A syringe is used to introduce incremental volumes of SO₂ limiting the maximum SO₂ concentration in the chamber and assuring safety of the subject. A Titrilog SO₂ analyzer with its rapid response characteristics provides quick measurement of the SO₂ concentration. The body plethysmograph used in this manner serves simultaneously as a pulmonary function measuring device and as an exposure chamber.     

Supply Curves for Using Powder River Basin Coal to Reduce Sulfur Emissions

Abstract

Supply curves were prepared for coal-fired power plants in the contiguous United States switching to Wyoming's Powder River Basin (PRB) low-sulfur coal. Up to 625 plants, representing ～44% of the nameplate capacity of all coal-fired plants, could switch. If all switched, more than $8.8 billion additional capital would be required and the cost of electricity would increase by up to $5.9 billion per year, depending on levels of plant derating. Coal switching would result in sulfur dioxide (SO₂) emissions reduction of 4.5 million t/yr. Increase in cost of electricity would be in the range of 0.31-0.73 cents per kilowatt-hour. Average cost of S emissions reduction could be as high as $1298 per t of SO₂. Up to 367 plants, or 59% of selected plants with 32% of 44% nameplate capacity, could have marginal cost in excess of $1000 per t of SO₂. Up to 73 plants would appear to benefit from both a lowering of the annual cost and a lowering of SO₂ emissions by switching to the PRB coal.     

Spatial variability of sulfur dioxide and sulfate over complex terrain in East Tennessee,USA

In 2004 and 2005, the East Tennessee Ozone Study (ETOS) enhanced its regional measurement program with annular denuder systems to quantify sulfur dioxide (SO₂) and PM_2.5 sulfate (SO₄^2?) at five sampling sites that were representative of the complex terrain and physiographic features of East Tennessee. Intersite spatial variability was more defined for SO₂ than for SO₄^2?, which showed a fairly uniform structure in both daytime and nighttime measurements. Pollution roses indicated that two sites may have been influenced by the proximity of SO₂ emission sources. The data suggest that SO₂ is affected by nearby sources in the study area while the sources of SO₄^2? are regionally distributed.     

Discharge Electrodes and Electrostatic Precipitators

Controlled fumigation experiments were conducted to determine the dose-response relationships for four species of urban trees exposed to sulfur dioxide. The species chosen were ginkgo, Norway maple, pin oak, and Chinese elm.

Results indicated that resistance to SO₂ increased among the species in the following order: Chinese elm, Norway maple, ginkgo, pin oak. Elm showed almost 100% leaf necrosis at exposures over 2 ppm for 6 hr, and severe chlorosis and necrosis at 0.25 ppm for 30 days. Fifty per cent leaf necrosis occurred on Norway maple at 3 ppm for 6 hr, and on ginkgo at 4 ppm for 6 hr, and both species developed moderate marginal chlorosis at 0.50 ppm for 30 days. Injury on pin oak was minor, even at 8 ppm for 8 hr, but at 0.50 ppm for 30 days, a slight overall chlorosis developed on the leaves.

The relative susceptibilities of the four species were the same in the long-term as in the short-term exposures. The shapes of the dose-response surfaces indicated that duration of exposure and concentration of the pollutant were of equal importance in producing injury on Chinese elm and probably on pin oak, but on Norway maple and ginkgo, concentration of SO₂ was of greater importance than the duration of exposure.     

The Absorption of Atmospheric Sulfur Dioxide by Water Solutions

Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water, over the range of atmospheric concentrations of 0.81?8.73 mg SO₂/M³, is a function of the concentration of SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmospheric SO₂. The pH of the exposed water samples reached values of 4.0 or less, comparable to values observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in distilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.