Sulfur atmospheric sources

Although there have only been a few studies to date, it has been suggested that coastal plumes (Turner et al., 1996 Simo et al., 1997) and estuaries (Iverson et al., 1989 Cerqueira and Pio, 1999) may be important atmospheric sources of DMS. DMS, a compound produced by certain phytoplankton, has been shown to have possible implications for climate control once released into the atmosphere (Charlson et al., 1987). DMS is formed by cleavage of dimethylsulfoniopropionate (DMSP) (Kiene, 1990). In fact, DMSP, shown to be correlated with bacterial activity, may provide as much as 100% of the sulfur and 3.4% of the carbon required for bacterial growth in oceanic waters (Kiene and Linn, 2000). Other sulfur compounds such as COS and carbon disulfide (CS2) have also been shown to be possible sources of S in estuaries. For example, significant concentrations of COS and CS2 were found in four European estuaries, 220 150 and 25 6 pM (Sciare et al., 2002). COS is the most abundant sulfur compound in the... 

Although there have been only a few studies to date, it has been suggested that coastal plumes and estuaries may be important atmospheric sources of DMS. Other sulfur compounds such as carbonyl sulfide (OCS) and carbon disulfide (CS2) have also been shown to possible sources of S in estuaries. 

In recent reviews, Kellogg, Cadle, Allen, Lazrus, and Martell (138) and Robinson and Robbins (214) discussed both atmospheric sources and sinks for sulfur compounds and a general atmospheric sulfur cycle. This section... 

Intensive investigations of the sulfur dynamics of forest ecosystems in the last decade can be attributed to the dominant role of sulfur as a component of acidic deposition. Studies in forested catchments include Fuller et al. (1986), Mitchell et al. (1989), Stam et al. (1992), and Andersson et al. (1992). Sulfur with a distinctive isotopic composition has been used to identify pollution sources (Krouse et al., 1984), and has been added as a tracer (Legge and Krouse, 1992 Mayer et al., 1992, 1993). Differences in the natural abundances can also be used in systems where there is sufhcient variation in the 5 " S of ecosystem components. Rocky Mountain lakes (USA), thought to be dominated by atmospheric sources of sulfate, have different 5 " S values than lakes believed to be dominated by watershed sources of sulfate (Turk et al., 1993). 

Acid rain is caused primarily by sulfur dioxide emissions from burning fossil fuels such as coal, oil, and natural gas. Sulfur is an impurity in these fuels for example, coal typically contains 2-3% by weight sulfur. Other sources of sulfur include the industrial smelting of metal sulfide ores to produce the elemental metal and, in some parts of the world, volcanic eruptions. When fossils fuels are burned, sulfur is oxidized to sulfur dioxide (SO2) and trace amounts of sulfur trioxide (S03)J21 The release of sulfur dioxide and sulfur trioxide emissions to the atmosphere is the major source of acid rain. These gases combine with oxygen and water vapor to form a fine mist of sulfuric acid that settles on land, on vegetation, and in the ocean. 

The study of the atmospheric sulfur cycle is a rapidly expanding field because human activity provides an important sulfur dioxide source. In the atmosphere S02 is converted to sulfate containing aerosol particles which can modify the radiation balance of the Earth-atmosphere system, the optical properties and the precipitation forming ability24 of the air. 

Sulfur deficiencies can readily develop, particularly in humid areas and areas that do not receive S from the atmosphere or from S-containing fertilizers. Atmospheric sources of S are organic S compounds emitted from marine plankton and inorganic S from oil and coal combustion. Because enforcement of environmental laws and better technologies have reduced the amount of S that soils receive through add rain, this source has decreased. 

Selection of pollution control methods is generally based on the need to control ambient air quaUty in order to achieve compliance with standards for critetia pollutants, or, in the case of nonregulated contaminants, to protect human health and vegetation. There are three elements to a pollution problem a source, a receptor affected by the pollutants, and the transport of pollutants from source to receptor. Modification or elimination of any one of these elements can change the nature of a pollution problem. For instance, tall stacks which disperse effluent modify the transport of pollutants and can thus reduce nearby SO2 deposition from sulfur-containing fossil fuel combustion. Although better dispersion aloft can solve a local problem, if done from numerous sources it can unfortunately cause a regional one, such as the acid rain now evident in the northeastern United States and Canada (see Atmospheric models). References 3—15 discuss atmospheric dilution as a control measure. The better approach, however, is to control emissions at the source. 

A smaller factor in ozone depletion is the rising levels of N2O in the atmosphere from combustion and the use of nitrogen-rich fertilizers, since they ate the sources of NO in the stratosphere that can destroy ozone catalyticaHy. Another concern in the depletion of ozone layer, under study by the National Aeronautics and Space Administration (NASA), is a proposed fleet of supersonic aircraft that can inject additional nitrogen oxides, as weU as sulfur dioxide and moisture, into the stratosphere via their exhaust gases (155). Although sulfate aerosols can suppress the amount of nitrogen oxides in the stratosphere... 

Sulfur dioxide occurs in industrial and urban atmospheres at 1 ppb—1 ppm and in remote areas of the earth at 50—120 ppt (27). Plants and animals have a natural tolerance to low levels of sulfur dioxide. Natural sources include volcanoes and volcanic vents, decaying organic matter, and solar action on seawater (28,290,291). Sulfur dioxide is beHeved to be the main sulfur species produced by oxidation of dimethyl sulfide that is emitted from the ocean. 

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

The reaction rates for oxidation of atmospheric SO2 (0.05-0.5 d ) yield a sulfur residence time of several days, at most this corresponds to a transport distance of several hundred to 1000 km. The formation of HNO by oxidation is more rapid and, compared with H2SO2P results in a shorter travel distance from the emission source. H2SO4 can also react with NH to form NH HSO or (NH2 2S04 aerosols. In addition the NH NO aerosols are in equihbrium with NH (g) and HNO (g). 

Equilibrium moisture content of a hygroscopic material may be determined in a number of ways, the only requirement being a source of constant-temperature and constant-humidity air. Determination may be made under static or dynamic conditions, although the latter case is preferred. A simple static procedure is to place a number of samples in ordinaiy laboratoiy desiccators containing sulfuric acid solutions of known concentrations which produce atmospheres of known relative humidity. The sample in each desiccator is weighed periodically until a constant weight is obtained. Moisture content at this final weight represents the equilibrium moisture content for the particular conditions. 

A substantial portion of fhe gas and vapors emitted to the atmosphere in appreciable quantity from anthropogenic sources tends to be relatively simple in chemical structure carbon dioxide, carbon monoxide, sulfur dioxide, and nitric oxide from combustion processes hydrogen sulfide, ammonia, hydrogen chloride, and hydrogen fluoride from industrial processes. The solvents and gasoline fractions that evaporate are alkanes, alkenes, and aromatics with relatively simple structures. In addition, more complex... 

Under low-dose conditions, forest ecosystems act as sinks for atmospheric pollutants and in some instances as sources. As indicated in Chapter 7, the atmosphere, lithosphere, and oceans are involved in cycling carbon, nitrogen, oxygen, sulfur, and other elements through each subsystem with different time scales. Under low-dose conditions, forest and other biomass systems have been utilizing chemical compounds present in the atmosphere and releasing others to the atmosphere for thousands of years. Industrialization has increased the concentrations of NO2, SO2, and CO2 in the "clean background" atmosphere, and certain types of interactions with forest systems can be defined. 

Forest systems also act as sources of CO2 when controlled or uncontrolled burning and decay of litter occur. In addition, release of ethylene occurs during the flowering of various species. One additional form of emission to the atmosphere is the release of pollen grains. Pollen is essential to the reproductive cycle of most forest systems but becomes a human health hazard for individuals susceptible to hay fever. The contribution of sulfur from forests in the form of dimethyl sulfide is considered to be about 10-25% of the total amount released by soils and vegetation (12). 

The chemical composition of particulate pollutants is determined in two forms specific elements, or specific compounds or ions. Knowledge of their chemical composition is useful in determining the sources of airborne particles and in understanding the fate of particles in the atmosphere. Elemental analysis yields results in terms of the individual elements present in a sample such as a given quantity of sulfur, S. From elemental analysis techniques we do not obtain direct information about the chemical form of S in a sample such as sulfate (SO/ ) or sulfide. Two nondestructive techniques used for direct elemental analysis of particulate samples are X-ray fluorescence spectroscopy (XRF) and neutron activation analysis (NAA). 

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