Aerosols fundamentals

Abstract Key features of tropospheric photochemistry are highlighted including both homogeneous gas-phase and heterogeneous reactions that are important in clouds and haze aerosol. Fundamental aspects of photochemical kinetics are reviewed and then extended to the major chromophores present in the multi-phasic, tropospheric atmosphere. Tables of up-to-date absorption cross sections and quantum yields as a function of wavelength range are presented. Primary emphasis is placed on reactions occurring within the troposphere and within clouds. 

There are numerous pertinent and systematic tie-ins between project-oriented aerosol work and basic physical investigations which are themselves quite closely akin to much classical and current work in physical science. The most significant aspect of these tie-ins is their potential for making substantial contributions to the functional needs of the applications areas while stimulating significant questions of basic physics. For this to be possible, it is necessary that the most relevant areas of physics be identified in such a manner as to make clear their relevance for aerosol-related studies and vice versa. Thus, these books differ from perhaps all others in that they are actually physics books whose topics are chosen for the central roles they play in that physical system commonly known as the aerosol. Fundamental, specifically aerosol questions have not been discussed in detail because of the editor s conviction that their complete description lies in the application of one or more of the domains identified in these books. The extent to which these books not only serve to identify the classes of physical questions that must be asked before any aerosol system can be measured, modelled, or otherwise described but also help to provide the link between selected basic physical disciplines and their applications will ultimately determine their contributions to both aerosol science and to physics. 

An interesting example of a large specific surface which is wholly external in nature is provided by a dispersed aerosol composed of fine particles free of cracks and fissures. As soon as the aerosol settles out, of course, its particles come into contact with one another and form aggregates but if the particles are spherical, more particularly if the material is hard, the particle-to-particle contacts will be very small in area the interparticulate junctions will then be so weak that many of them will become broken apart during mechanical handling, or be prized open by the film of adsorbate during an adsorption experiment. In favourable cases the flocculated specimen may have so open a structure that it behaves, as far as its adsorptive properties are concerned, as a completely non-porous material. Solids of this kind are of importance because of their relevance to standard adsorption isotherms (cf. Section 2.12) which play a fundamental role in procedures for the evaluation of specific surface area and pore size distribution by adsorption methods. 

Simulation of aerosol processes within an air quaUty model begins with the fundamental equation of aerosol dynamics which describes aerosol transport (term 2), growth (term 3), coagulation (terms 4 and 5), and sedimentation (term 6) ... 

For determination of the aerodynamic diameters of particles, the most commonly apphcable methods for particle-size analysis are those based on inertia aerosol centrifuges, cyclones, and inertial impactors (Lundgren et al.. Aerosol Measurement, University of Florida, Gainesville, 1979 and Liu, Fine Paiiicles—Aerosol Generation, Measurement, Sampling, and Analysis, Academic, New York, 1976). Impactors are the most commonly used. Nevertheless, impactor measurements are subject to numerous errors [Rao and Whitby, Am. Ind. Hyg. A.s.soc.]., 38, 174 (1977) Marple and WiUeke, "Inertial Impactors, in Lundgren et al.. Aerosol Measurement and Fuchs, "Aerosol Impactors, in Shaw, Fundamentals of Aerosol Sci-... 

These fundamental equations apply to many systems involving diserete entities aerosols, moleeules, and partieles, even people. A full review of their derivation of these equations is to be found in Randolph and Larson (1988), who have pioneered their applieation to industrial erystallizers in partieular. 

The two fundamental theories for calculating the attachment coefficient, 3, are the diffusion theory for large particles and the kinetic theory for small particles. The diffusion theory predicts an attachment coefficient proportional to the diameter of the aerosol particle whereas the kinetic theory predicts an attachment coefficient proportional to the aerosol surface area. The theory... 

It is the purpose of this chapter to summarize knowledge dealing with the role of electrostatic phenomena in particulate systems, especially in aerosols. A relatively comprehensive annotated bibliography by Blake and Lapple (BIO) has surveyed the bulk of the literature through 1965. This chapter cites and summarizes the results of the more important or directly relevant work in this field.1 However, before considering specific phenomena, it is desirable to review some of the fundamental principles in the field of electrostatics. 

FUNDAMENTALS of AEROSOL BEHAVIOR, Wiley-Interscience, New York,... 

There are two general types of aerosol source apportionment methods dispersion models and receptor models. Receptor models are divided into microscopic methods and chemical methods. Chemical mass balance, principal component factor analysis, target transformation factor analysis, etc. are all based on the same mathematical model and simply represent different approaches to solution of the fundamental receptor model equation. All require conservation of mass, as well as source composition information for qualitative analysis and a mass balance for a quantitative analysis. Each interpretive approach to the receptor model yields unique information useful in establishing the credibility of a study s final results. Source apportionment sutdies using the receptor model should include interpretation of the chemical data set by both multivariate methods. 

Urban aerosols are complicated systems composed of material from many different sources. Achieving cost-effective air particle reductions in airsheds not meeting national ambient air quality standards requires identification of major aerosol sources and quantitative determination of their contribution to particle concentrations. Quantitative source Impact assesment, however, requires either calculation of a source s impact from fundamental meteorological principles using source oriented dispersion models, or resolving source contributions with receptor models based on the measurement of characteristic chemical and physical aerosol features. Q)... 

Particulate carbon in the atmosphere exists predominantly in three forms elemental carbon (soot) with attached hydrocarbons organic compounds and carbonates. Carbonaceous urban fine particles are composed mainly of elemental and organic carbon. These particles can be emitted into the air directly in the particulate state or condense rapidly after Introduction into the atmosphere from an emission source (primary aerosol). Alternatively, they can be formed in the atmosphere by chemical reactions involving gaseous pollutant precursors (secondary aerosol). The rates of formation of secondary carbonaceous aerosol and the details of the formation mechanisms are not well understood. However, an even more fundamental controversy exists regarding... 

Friedlander, S. K., Smoke, Dust, and Haze Fundamentals of Aerosol Behavior, Wiley-Interscience, New York, 1977. 

It is well established that in non-arid regions, precipitation is the primary means by which contaminating aerosols are removed from the atmosphere. Many chemical, physical, and meteorological parameters affect the micro, meso, and synoptic scale processes through which precipitation transports radioactive aerosols from atmosphere to ground. These parameters include the radioactivity component of the natural aerosols, the processes by which water vapor condenses and grows to raindrops, and the incorporation of the radioactive aerosol into the precipitation. Thus, the prediction of specific deposition from fundamental considerations has proved to be difficult because of the many uncertainties yet prevalent in these processes. Many attempts have been made to evaluate the deposition of these aerosols by empirical studies. 

The fact that fine atmospheric particles are enriched in a number of toxic trace species has been known since the early 1970s. Natusch and Wallace (20, 21) observed that the fine particles emitted by a variety of high-temperature combustion sources follow similar trends of enrichment with decreasing particle size as observed in the atmosphere, and they hypothesized that volatilization and condensation of the trace species was responsible for much of the enrichment. Subsequent studies of a number of high-temperature sources and fundamental studies of fine-particle formation in high-temperature systems have substantiated their conclusions. The principal instruments used in those studies were cascade impactors, which fractionate aerosol samples according to the aerodynamic size of the particles. A variety... 

The arsenal of aerosol measurement methods has expanded dramatically over recent years, but a number of needs for fundamental research into the nature and origins of the atmospheric aerosol cannot be met by the current instrumentation. Instrumentation that has proven most valuable in the chemical characterization of the atmospheric aerosol is woefully inadequate either for following the chemical dynamics of aerosols because of the rapid changes that occur in homogeneous reacting systems or for unraveling the complexity of the aerosol products. 

Al fundamental question about the interpretation of acidic aerosol data is whether researchers can characterize past and current atmospheric concentrations and distributions (spatial and temporal) with sufficient accuracy for studies of their effects on ecosystems and human health. Part of the answer to this question can be provided by a review of the methods that have been used to measure the strong acid content of aerosol particles collected from the atmosphere. This chapter serves as such a review, and, in evaluating analytical procedures, it specifically assesses the ability of each procedure to overcome sampling artifacts, to distinguish between strong and weak acids, to properly partition strong acidity between gas-phase and aero-sol-phase species, and to quantitate strong acidity at the levels at which it is found in the ambient atmosphere. 

The wide use of spray injection for the introduction of reactants into combustion chambers has pointed to the need for an analysis of the processes which govern combustion of liquid aerosols. This review presents the theoretical and experimental aspects involved in the burning of a single droplet. The application of the results obtained for a single droplet to the burning characteristics of liquid sprays remains a problem of fundamental importance in combustion research. 

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