Sulfur oxidation, atmospheric

In the atmosphere, sulfur oxides can combine with water and oxygen to form sulfurous and sulfuric acids. The deposition of these acids causes corrosion or decomposition of materials such as limestone, marble, iron, and steel. The deterioration of building facades and monuments is one result of this worldwide problem. Flushing of the sulfur oxides from the air by precipitation (acid rain) can lead to acidification of lakes and sods, weakening or killing plants and animals. 

Because of overmanuring of agricultural land, the ammonia content of the air has increased noticeably for example, by a factor of 2-3 in rainwater in the United Kingdom between 1%8 and 1978 (Martin and Barber, 1978). Ammonia in atmospheric quantities does not accelerate zinc corrosion, and petrochemical plants where ammonium salts are present show no accelerated attack on galvanized steel. However, ammonia will react with atmospheric sulfur oxides, yielding ammonium sulfate, which accelerates paint film corrosion and also zinc corrosion. 

Atmospheric sulfur oxides (sulfur dioxide and sulfur trioxide) primarily come from the combustion of sulfur-containing coal [36]. Inhalation of sulfur dioxide rapidly causes the onset of bronchospastic effects after exposure [32]. 

Ware, J. H., Thibodeau, L. A., Speizer, F. E., Colome, S., Ferris, B. G., Jr. 1981. Assessment of the health effects of atmospheric sulfur oxides and particulate matter evidence from observational studies. Environ. Health Persp. 41 255-76. 

Hafnium metal is analy2ed for impurities using analytical techniques used for 2irconium (19,21,22). Carbon and sulfur in hafnium are measured by combustion, followed by chromatographic or in measurement of the carbon and sulfur oxides (19). Chromatographic measurement of Hberated hydrogen follows the hot vacuum extraction or fusion of hafnium with a transition metal in an inert atmosphere (23,24). 

G. M. YEAy, Atmospheric Sulfur andNitrogen Oxides Eastern North American Source Eeceptor Relationships, Academic Press, Orlando, Fla., 1994. 

Sulfur oxides (SO,) are compounds of sulfur and oxygen molecules. Sulfur dioxide (SO2) is the predominant form found in the lower atmosphere. It is a colorless gas that can be detected by taste and smell in the range of 1, (X)0 to 3,000 uglm. At concentrations of 10,000 uglm , it has a pungent, unpleasant odor. Sulfur dioxide dissolves readily in water present in the atmosphere to form sulfurous acid (H SOj). About 30% of the sulfur dioxide in the atmosphere is converted to sulfate aerosol (acid aerosol), which is removed through wet or dry deposition processes. Sulfur trioxide (SO3), another oxide of sulfur, is either emitted directly into the atmosphere or produced from sulfur dioxide and is readily converted to sulfuric acid (H2SO4). 

Health effects attributed to sulfur oxides are likely due to exposure to sulfur dioxide, sulfate aerosols, and sulfur dioxide adsorbed onto particulate matter. Alone, sulfur dioxide will dissolve in the watery fluids of the upper respiratory system and be absorbed into the bloodstream. Sulfur dioxide reacts with other substances in the atmosphere to form sulfate aerosols. Since most sulfate aerosols are part of PMj 5, they may have an important role in the health impacts associated with fine particulates. However, sulfate aerosols can be transported long distances through the atmosphere before deposition actually occurs. Average sulfate aerosol concentrations are about 40% of average fine particulate levels in regions where fuels with high sulfur content are commonly used. Sulfur dioxide adsorbed on particles can be carried deep into the pulmonary system. Therefore, reducing concentrations of particulate matter may also reduce the health impacts of sulfur dioxide. Acid aerosols affect respiratory and sensory functions. 

The gaseous component typically contains hydrocarbons, hydrogen sulfide, ammonia, mercaptans, solvents, and other constituents, and is either discharged directly to the atmosphere or is combusted in a flare. The major air emissions from blowdown systems are hydrocarbons in the case of direct discharge to the atmosphere and sulfur oxides when flared. 

Sulfur oxide emissions enter the atmosphere from a variety of sources, some of human origin, others of natural origin. The main sulfur oxide is sulfur dioxide, or SO,. 

High levels of sulfur not only form dangerous oxides, but they also tend to poison the catalyst in the catalytic converter. As it flows over the catalyst in the exliaust system, the sulfur decreases conversion efficiency and limits the catalyst s oxygen storage capacity. With the converter working at less than maximum efficiency, the exhaust entering the atmosphere contains increased concentrations, not only of the sulfur oxides but also, of hydrocarbons, nitrogen oxides, carbon monoxides, toxic metals, and particulate matter. 

The process will adversely affect air quality by releasing nitrogen oxides, sulfur oxides, carbon monoxides and other particulates into the atmosphere. Better control of the conversion conditions and better control of emissions can make the process cleaner, yet technology cannot do anything to curb carbon emissions. Since much of the carbon in coal is converted to carbon dioxide in the synthesis process, and is not part of the synthetic fuel itself, the amount of carbon dioxide that will be released to the environment during combustion is 50 to 100 percent more than coal, and around three times more than natural gas. 

Precipitation over North America gradually becomes more acidic from west to east, especially in industrialized areas of the Northeast. This acid rain may be a result of the release of nitrogen and sulfur oxides into the atmosphere. The colors and numbers (see key) indicate pH measured at field laboratories in 2004. Data from National Atmospheric Deposition Program/National Trends Network http //nadp.sws.uiuc.edu. 

Industry and transport contribute another 1.5 X 1011 kg of the dioxide, of which about 70% comes from oil and coal combustion—mainly in electricity-generating plants. Because, like many other countries, both the United States and Canada have increased restrictions on emissions of sulfur oxides, emissions of S02 into the atmosphere in Canada fell 50% between 1980 and 2000 and in the United States they fell 40% during the same period (see Box 10.1). 

Figure 4-13 shows an example from a three-dimensional model simulation of the global atmospheric sulfur balance (Feichter et al, 1996). The model had a grid resolution of about 500 km in the horizontal and on average 1 km in the vertical. The chemical scheme of the model included emissions of dimethyl sulfide (DMS) from the oceans and SO2 from industrial processes and volcanoes. Atmospheric DMS is oxidized by the hydroxyl radical to form SO2, which, in turn, is further oxidized to sulfuric acid and sulfates by reaction with either hydroxyl radical in the gas phase or with hydrogen peroxide or ozone in cloud droplets. Both SO2 and aerosol sulfate are removed from the atmosphere by dry and wet deposition processes. The reasonable agreement between the simulated and observed wet deposition of sulfate indicates that the most important processes affecting the atmospheric sulfur balance have been adequately treated in the model. 

There is a large variety of atmospheric sulfur compounds, in the gas, solid, and liquid phases. Table 7-3 lists a number of gaseous compounds, range of concentration, source, and sink (where known). As this list illustrates, a significant number of these gases contribute to the existence of oxidized sulfur in the forms of SO2 and sulfate aerosol particles. Table 7-4 lists the oxy-acids of sulfur and their ionized forms that could exist in the atmosphere. Of these the sulfates certainly are dominant, with H2SO4 and its products of neutralization with NH3 as the most frequently reported forms. 

Acid rain is actually a catchall phrase for any kind of acidic precipitation, including snow, sleet, mist, and fog. Acid rain begins when water comes into contact with sulfur and nitrogen oxides in the atmosphere. These oxides can come from natural sources such as volcanic emissions or decaying plants. But there are man-made sources as well, such as power plant and automobile emissions. In the United States, two-thirds of all the sulfur dioxide and one-fourth of the nitrogen oxides in the atmosphere are produced by coal-burning power plants. 

In simple terms, the global sulfur cycle has two components. One is biochemical involving the conversion of sulfate to sulfide and the formation of DMS the other is atmospheric photochemical oxidation of DMS to sulfur oxyacids. DMS is formed mainly in the oceans by microorganisms and to a lesser extent in plants. About 38M0 Tg year-1 of DMS are released to the atmosphere from the oceans. The major precursor for DMS formation is the sulfonium salt, dimethylsulfoniopropionate, (CH3)2 S+ CH2 CH2 COOH, DMSP. DMSP lyase enzymes catalyze an elimination of acrylic acid from DMSP (Equation 12) with the release of DMS ... 

Historically, the sulfur oxides have long been known to have a deleterious effect on the atmosphere, and sulfuric acid mist and other sulfate particulate matter are well established as important sources of atmospheric contamination. However, the atmospheric chemistry is probably not as well understood as the gas-phase photoxidation reactions of the nitrogen oxides-hydrocarbon system. The pollutants form originally from the S02 emitted to the air. Just as mobile and stationary combustion sources emit some small quantities of N02 as well as NO, so do they emit some small quantities of S03 when they bum sulfur-containing fuels. Leighton [2] also discusses the oxidation of S02 in polluted atmospheres and an excellent review by Bulfalini [3] has appeared. This section draws heavily from these sources. 

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