Atmospheric aerosol sulfate, source

A good atmospheric example of the above particle formation is the production of sulfate particles from gaseous precursors (see Subsection 3.6.3). It is further believed that the smaller organic particles discussed in Subsection 3.3.3 are also formed by gas-to-particle conversion. However, a large quantity of aerosol particles can form during the cooling of vapours with low saturation pressure, which are produced by combustion processes. This aerosol formation is obvious in urban and industrial environments. However, natural forest, brush and grass fires also provide an important atmospheric aerosol particle source (see Cadle, 1973). 

This global average burden of anthropogenic sulfate aerosol can be estimated by considering the entire atmospheric volume as a box. Because the lifetime of sulfate aerosol is short, the sum of all sulfate sources, Q, and its lifetime in the box, f, along with the area of the earth, determine B ... 

Atmospheric aerosols have a direct impact on earth s radiation balance, fog formation and cloud physics, and visibility degradation as well as human health effect[l]. Both natural and anthropogenic sources contribute to the formation of ambient aerosol, which are composed mostly of sulfates, nitrates and ammoniums in either pure or mixed forms[2]. These inorganic salt aerosols are hygroscopic by nature and exhibit the properties of deliquescence and efflorescence in humid air. That is, relative humidity(RH) history and chemical composition determine whether atmospheric aerosols are liquid or solid. Aerosol physical state affects climate and environmental phenomena such as radiative transfer, visibility, and heterogeneous chemistry. Here we present a mathematical model that considers the relative humidity history and chemical composition dependence of deliquescence and efflorescence for describing the dynamic and transport behavior of ambient aerosols[3]. 

Atmospheric aerosols are complex mixtures of particles derived from diverse sources. Soot from diesel engines, fly ash from coal combustion, and sulfates, nitrates, and organic compounds produced by atmospheric reactions of gaseous pollutants all contribute to the aerosol. Particle size and composition depend upon the conditions of aerosol formation and growth and determine the effects of atmospheric aerosols on human health, ecosystems, materials degradation, and visibility. Much of the research on environmental aerosols has focused on fine particles ranging from a few micrometers in... 

As Michalski and Thiemens (2000) have shown, aerosol nitrate possesses an extraordinarily large mass-independent isotopic composition. As for aerosol sulfate, this isotopic signature has already been shown to provide a new means to elucidate source and chemical transformation processes. This has proved to be an important technique by which the nitrate biogeochemical cycle may be understood further. For example, the massive mass-independent isotopic signature observed in Chilean desert nitrates uniquely reveals that these nitrates must be atmospherically derived since all other sources (by measurement) possess mass-dependent isotopic compositions. In addition, these measurements, coupled with contemporary aerosol nitrate measurements reveal that the oxygen isotopic signatures are stable on million year timescales. This is particularly valuable, as this permits measurement of nitrate in polar ice samples to examine paleo-variations in nitrate and in general, chemistry. As... 

NH3 and to a lesser extent mono-, di-, and trimethylamines are the only significant gaseous bases in the atmosphere, and there has been considerable interest in whether the oceans are a source or sink of these gases. Early attempt to assess the air-sea flux from concentration measurements are probably suspect because of the ease with which sample contamination can occur during laboratory processing and analysis. It should be noted here that due to its high solubihty (low value of Henry s law constant), the air-water transfer of NH3 (and the methylamines for the same reason) is under gas phase control (see Section 6.03.2.1.1). The first reliable measurements were probably from the North and South Pacific and indicated that the flux of NH3 from sea to air is of a size similar to that for emission of DMS (Quinn et al., 1990, 1988). Indeed, the authors showed that this similarity was mirrored in the molar ratio of (non-sea-salt) sulfate to ammonium (1.3 0.7) in atmospheric aerosol particles collected on the cruise, indicating that for clean marine air remote from terrestrial sources, the emission of DMS and NH3 from the sea appears to control the composition of the aerosol. 

An important example related lo the atmospheric aerosol is the droplet containing dissolved sulfates that form as a result of the oxidation of SO2 in solution. The sulfates may be present a.s sulfuric acid or in a partially neutralized form as ammonium salts or metallic salts from sources such as flyash. The droplet size distribution and chemical composition are determined by a combination of thermodynamic and rate processes. In this section, we consider only equilibrium thermodynamics as it affects the vapor pressure of the drop. 

Arimoto R, Ray BJ, Duce RA et al (1990) Concentrations, sources, and fluxes of trace-elements in the remote marine atmosphere of New Zealand. J Geophys Res 95 22389-22405 Arimoto R, Duce RA, Savoie DL et al (1992) Trace-elements in aerosol-particles from Bermuda and Barbados—concentrations, sources and relationships to aerosol sulfate. J Atmos Chem 14 439 57... 

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... 

DMS has been observed in the marine atmosphere since the early 1970s, but it was not until the mid-1980s that there was interest in this gas as being a natural source for sulfate CCN. Sulfate aerosols are, in number terms, the dominant source of CCN. The major role clouds play in the climate system leads to possible climatic implications if changes to DMS production occurred. Furthermore, the dependence of this production on environment conditions means that scope for a feedback process arises this feedback is called the Charlson hypothesis. ... 

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. 

Considerable time elapsed before there was general acceptance of Haagen-Smit s important discovery, in part because of its subtle nature. For the first time, a major air pollution problem was demonstrated to be caused by a pollutant generated in the atmosphere. Its effect often did not become apparent until many miles downwind from the source. (The same suspicion has been attached to sulfate-containing aerosols for many years, but the proof that the sulfate is damaging is not as well established.) In addition, a new pollution source, automobile exhaust, had been shown to be of prime importance. 

The primary sources that are responsible for the presence of this family of compounds in the atmosphere emit NH3, N20, and NO to the troposphere, the lowest level of the atmosphere, which extends to approximately 10 km from the earth s surface. NH3 seems to undergo very little chemistry in the atmosphere except for the formation of aerosols, including ammonium nitrate and sulfates. NH3 and the aerosols are highly soluble and are thus rapidly removed by precipitation and deposition to surfaces. N20 is unreactive in the troposphere. On a time scale of decades it is transported to the stratosphere, the next higher atmospheric layer, which extends to about 50 km. Here N20 either is photodissociated or reacts with excited oxygen atoms, O (lD). The final products from these processes are primarily unreactive N2 and 02, but about 10% NO is also produced. The product NO is the principal source of reactive oxidized nitrogen species in the stratosphere. 

CCN). Changes in the concentrations of CCN may alter the cloud droplet concentration, the droplet surface reflectivity, the radiative properties of clouds (cloud albedo) (2), and hence, the earth s climate (8-101. This mechanism has been proposed for the remote atmosphere, where the radiative properties of clouds are theoretically predicted to be extremely sensitive to the number of CCN present (ID). Additionally, these sulfate particles enhance the acidity of precipitation due to the formation of sulfuric acid after cloud water dissolution (11). The importance of sulfate aerosol particles to both radiative climate and rainwater acidity illustrates the need to document the sources of sulfur to the remote atmosphere. 

Atmospheric Oxidation of SOo to Sulfate. Regardless of the source, sulfur dioxide is oxidized under atmospheric conditions in the gas phase, cloud droplets or on the surface of wet aerosol particles. The gas phase reaction (Equation 4)... 

The major source of sulfate aerosols appears to be the oxidation of atmospheric I S and S02. While some is also produced by sea spray, most of the sea-salt aerosol returns directly to the ocean, resulting in only a small net production. 

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