Secondary aerosol particulate

Environmental Aspects. Airborne particulate matter (187) and aerosol (188) samples from around the world have been found to contain a variety of organic monocarboxyhc and dicarboxyhc acids, including adipic acid. Traces of the acid found ia southern California air were related both to automobile exhaust emission (189) and, iadirecfly, to cyclohexene as a secondary aerosol precursor (via ozonolysis) (190). Dibasic acids (eg, succinic acid) have been found even ia such unlikely sources as the Murchison meteorite (191). PubHc health standards for adipic acid contamination of reservoir waters were evaluated with respect to toxicity, odor, taste, transparency, foam, and other criteria (192). BiodegradabiUty of adipic acid solutions was also evaluated with respect to BOD/theoretical oxygen demand ratio, rate, lag time, and other factors (193). 

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... 

Turpin, B. J., J. J. Huntzicker, S. M. Larson, and G. R. Cass, Los Angeles Summer Midday Particulate Carbon Primary and Secondary Aerosol, Environ. Sci. Technoi, 25, 1788-1793 (1991). 

Keywords Aerosol, Emission sources, Greece, Mediterranean Basin, Particulate matter, Road dust, Sahara dust, Secondary aerosol, Ship emissions... 

The major processes for creating atmospheric fine particles (diameter < 2.5 pm) are combustion and gas-to-particle conversion (GPC). Whereas combustion particles are emitted directly to the atmosphere (primary aerosol), gas-to-particle conversion refers to the chemistry that leads to particulate matter by converting volatile gases into condensable substances under atmospheric conditions. Gas-to-particle conversion leads to an increase in the mass of preexisting particles and under some circumstances may lead to the creation of new particles. Particulate material produced by GPC is referred to as secondary aerosol. 

Sea spray, volcanic eruptions, soil dust, as well as some industries (cement manufacturing) produce the so called primary aerosols, i.e. the material is emitted directly in particulate state (Klockow, 1982), and they are both line and coarse. Secondary aerosols are produced in the atmosphere usually by eondensation after emission from high temperature sources, and they are fine as a rule. Considering the difference in the chemical composition it is recognized that the major components of the fine aerosols are toxie substances of anthropogenic origin such as As, Cd, Pb, Se, Zn etc. while the course aerosols are enriched in elements like Ca, Fe, Si coming from erosion, sea aerosols and other natural sources. 

Particles in the atmosphere arise from natural sources, such as windborne dust, sea spray, and volcanoes, and from anthropogenic activities, such as combustion of fuels. Whereas an aerosol is technically defined as a suspension of fine solid or liquid particles in a gas, common usage refers to the aerosol as the particulate component only (Table 2.17). Emitted directly as particles (primary aerosol) or formed in the atmosphere by gas-to-particle conversion processes (secondary aerosol), atmospheric aerosols are generally considered to be the particles that range in size from a few nanometers (nm) to tens of micrometers... 

Aerosols that are created in the atmosphere, by nucleation and growth from chemicals in the atmosphere, are termed seco / ry aerosols. An example of a secondary aerosol is the dispersed particulate matter that forms in the atmosphere due to free-radical polymerization of automobile exhaust gases [119]. Another example is the sulfates produced in the atmosphere from the SO2 gas released by industrial plants. These sulfate particles reflect sunlight and also serve as nuclei for cloud formation (see Section 9.7.1). 

Inorganic and organic aerosols that are directly emitted into the atmosphere are known as primary aerosols, for example, aerosols from ocean spray, volcanic eruptions or combustion. Those aerosols that are formed in the atmosphere through a sequence of chemical reactions are referred to as secondary aerosols, and they account for a major component of tropospheric particulates. 

The extent of gas-to-aerosol conversion of secondary pollutants can be estimated by measuring gas particle distribution factors for carbon, nitrogen, and sulfur species. For example, /c = P/ P + G), where P = particulate organic carbon ng/m as carbon) and G = gas-phase... 

Rosen, Hansen, Dod and Novakov found a high correlation between optical absorptivity and the particulate carbon loading in 24-h samples from several California cities ( 5). Elemental carbon, a primary pollutant which is directly related to the absorptivity, was found to be a large fraction of the carbonaceous aerosol. They were able to place a low limit on the amount of secondary organic aerosol produced in correlation with ozone. 

Secondary pollutants H2S04, sulfate aerosols, etc. 03, PAN, HNO, aldehydes, particulate nitrate and sulfate, etc. 

Stable aerosols of fine particulates as well as vapors constitute the greatest health risk because of the likelihood of pulmonary absorption. Correlations between trace element pollution and their concentrations in biological fluids or tissue are not uncommon and have been documented for arsenic (62) and lead (63). Man can absorb 75-85% of inhaled mercury vapor at concentrations of 50-350 pg/M3 (64) and even more at lower concentrations (65). Certain aerosols like vanadium, iron, manganese, and lead may contribute to the formation of secondary atmospheric pollutants (52, 66). 

Also special care should be taken to reduce uncertainties on emission data and measurements. The validation of an aerosol model requires the analysis of the aerosol chemical composition for the main particulate species (ammonium, sulphate, nitrate and secondary organic aerosol). To find data to perform this kind of more complete evaluation is not always easy. The same applies to emissions data. The lack of detailed information regarding the chemical composition of aerosols obliges modellers to use previously defined aerosols components distributions, which are found in the literature. Present knowledge in emission processes is yet lacunal, especially concerning suspension and resuspension of deposited particles [37]. 

Oxidation/hydroxylation of aromatic compounds by OH and HOONO is expected to enhance their degradation rate and hence decrease their lifetime on particulate matter, which in the case of pollutants is beneficial from the point of view of human health. Oxidation of PAHs could also lead to the production of photosensitizers such as quinones and aromatic carbonyls [10, 40, 41]. These compounds, if present in the gas phase, are also able to form aggregates and are therefore involved in the formation of secondary organic aerosol [42]. In contrast, nitration induced by OH + N02 or HOONO could lead to highly mutagenic nitro-PAHs [43] or phytotoxic nitrophenols [44, 45], in which case the health and environmental impact of the reaction intermediates is not negligible and is sometimes higher than that of the parent molecules. 

Atmospheric particles influence the Earth climate indirectly by affecting cloud properties and precipitation [1,2], The indirect effect of aerosols on climate is currently a major source of uncertainties in the assessment of climate changes. New particle formation is an important source of atmospheric aerosols [3]. While the contribution of secondary particles to total mass of the particulate matter is insignificant, they usually dominate the particle number concentration of atmospheric aerosols and cloud condensation nuclei (CCN) [4]. Another important detail is that high concentrations of ultrafine particles associated with traffic observed on and near roadways [5-7] lead, according to a number of recent medical studies [8-11] to adverse health effects. 

Comparison for total particulate matter is more problematic. Cases with dominant fire-induced pollution are reproduced comparatively well (Fig. 15.4) while the contributions of dust and secondary organic aerosol are currently missing from the system. The resulting problems are illustrated by the Fig. 15.5, which represents a full-year time series for a continental EMEP station from Germany. It is seen that... 

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