Crustal aerosol source

The average particle size distributions for four predominantly crustal elements, Al, Si, Ca, and Ti, are shown in Figure 3. They are essentially identical. It should be pointed out that the downturn of the relative concentrations above 8 ymad (impactor stage 6) is the combined result of the actual distribution of particle sizes in the atmosphere and the efficiency with which these very coarse particles can enter (upward) into the cascade impactor. This efficiency must decrease with increasing particle size and generally depend on inlet design and wind speed. Nevertheless, it is important to note here that the patterns of the four elements are similar, implying a common aerosol source. 

Iron was chosen as the reference element because its major source is likely to be soil and it is measured with good accuracy and precision by FIXE. Crustal abundances were taken from Mason (21). Enrichment factors greater than 1 indicate an enrichment of that element relative to crustal abundances values less than 1 indicate a depletion. The results of this calculation are shown in Table 4. For this calculation it was assumed that ammonium and nitrate accounted for all aerosol nitrogen. It is seen that Si and Ca are near their crustal abundance, indicating a probable soil dust source. The low EF for Al is probably due to a systematic error in the Al measurement rather than a true depletion. Potassium, although present in small concentrations, is slightly enriched relative to crust. The other fine aerosol species, C, N, S, and Pb are enriched by factors of thousands over their natural crustal abundance, indicating that they are not due to wind-blown dust. 

Figure 2 indicates Mn/Fe to be somewhat above the crustal ratio through 19 March, and thereafter a marked Increase is seen. The aerosol ratio Zn/Fe averages about 20 times greater than in the earth crust (somewhat greater on 20-21 March), showing "anomalous" atmospheric enrichment of Zn first recognized by Rahn (7). Since particle size distribution measurements, discussed below, show substantial fine particle concentrations of both Zn and Mn, the processes for their transfer to the atmosphere must be different from those for the other six elements of Figure 2. However, their concentration variations in time still resemble those of Fe shown in Figure 1 and therefore these elements may also be relatively large scale characteristics of air masses, in contrast to S where regional pollution sources and aerosol formation processes must be Important.

In a search for sources of alkaline materials in rural air and rain, we have sampled and performed multi-element analyses on ambient particulate matter and potential source materials. Ambient aerosols were sampled daily using single Nuclepore filters or Florida State University "streakers." Samples of soil and unpaved road materials were also collected and analyzed. The samples were analyzed by various multi-element methods, including ion-and proton-induced X-ray emission and X-ray fluorescence, as well as by atomic absorption spectrophotometry. Visual observations, as well as airborne elemental concentration distributions with wind direction and elemental abundances in aerosols and source materials, suggested that soil and road dust both contribute to airborne Ca. Factor analysis was able to identify only a "crustal" source, but a simple mass balance suggested that roads are the major source of Ca in rural central Illinois in summer. 

Abundances. Additional evidence of possible multiple sources comes from an examination of the mass percentages (abundances) of crustal elements in aerosol samples. Figures 6 through 11 show abundances for Al, Si, K, Ca, Ti, and Fe. 

Table 1) and the aerosol element abundances measured in the 36 Individual vane samples. The distributions of crustal element abundances in aerosols were shown in Figures 6-11 along with the respective abundances of the elements in the source materials. 

The results presented a variety of evidence for the identity of Ca sources near our rural sampling site. The distribution of mean crustal element concentrations as a function of wind direction in summer and fall, from the streaker data, suggest a combination of road and soil sources. This agrees with a comparison of crustal abundances in aerosols and source materials. The comparison showed that most of the elements examined had abundances in the aerosol that often fell between those characteristic of roads and soil. This was not the case for Si, but Si may be expected to be less abundant in aerosol samples than in bulk surficial materials because of the preponderance of quartz (Si02) in the larger particles. 

The concentration of metals in atmospheric aerosols and rainwater (Table 7.1) is therefore a function of their sources. This includes both the occurrence of the metals in combustion processes and their volatility, as well as their occurrence in crustal dust and seawater. As a result of this, the size distribution of different metals is very different and depends on the balance of these sources. For a particular metal this distinction is similar in most global locations (Table 7.2), although some variability does occur as wind speed and distance from source exert an influence on the particle size distribution spectrum (Slinn, 1983). Once in the atmosphere particles can change size and composition to some extent by condensation of water vapour, by coagulation with other particles, by chemical reaction, or by activation (when supersaturated) to become cloud or fog droplets (Andreae et al., 1986 Arimoto et al., 1997 Seinfeld and Pandis, 1998). 

Finally, in the case of present-day aerosol nitrate isotopic measurements, samples collected as a function of particle size provide another level of detection in the resolution of sources and atmospheric transformation mechanisms. Large particles (1-10 pm) typically are crustal or oceanic sea spray, depending upon where the particular samples are collected. Small particles (less than 0.1 pm) generally are gas-to-particle conversion process products. Using combined multi-isotope ratio measurements and size-fractionated collection processes, it is possible to provide sophisticated details of atmospheric aerosol fates. 

Figure 13.15 shows Ogi for various aerosol chemical components. Elements present in the primary emissions include the metals, silicon, and black carbon (BC). Among the primary aerosol emission sources are automotive emissions and tire wear, residual fuel oil combustion, crustal materials, and the marine aerosol. Despite the variety of primary emission sources, values of a,- fell within a narrow band, 1.8.5 0.14. Similar results were obtained for data. sets at other Los Angeles sites. Thus variations in the ambient... 

We turn next to consider the nonvolatile alkali and alkaline earth elements and the insoluble components of mineral origin. Their major natural sources are the Earth s crust and the ocean, respectively. We expect the chemical composition of the aerosol to reflect the relative contributions of elements from both reservoirs, provided other contributions from anthropogenic or volcanic sources are negligible. In Section 7.4.4 it has been noted, however, that his premise does not hold for all constituents of the aerosol. Some trace components are considerably enriched compared with their crustal abundances. It is appropriate, therefore, to inquire whether the observations confirm our expectations at least for the major elements listed in Table 7-13, or whether deviations occur also in these cases. As Rahn (1975a,b) has shown, the problem may be approached in two ways, either by calculating enrichment factors defined by... 

Hoffman et al. (1974) found the same procedure applicable to data obtained from measurements on board of ships in the central Atlantic Ocean. Table 7-15 includes mean (X)/(Na) ratios from their work. Shown in parentheses are the values derived from the slopes of regression lines. They are distinctly lower than the averaged data. Hoffman et al. (1974) measured also the abundance of iron in the aerosols. Since the samples were taken in a region partly affected by fallout from the Saharan dust plume, iron serves as a convenient indicator for the contribution of material from continental sources. Not surprisingly, the enrichment of the elements Mg, Ca, K, and Sr was well correlated with the iron content. The (X)/(Na) ratios approached those of sea water only when the Fe concentrations were very low. These results demonstrate that materials from both marine and crustal sources are present over the open ocean. In addition, they provide some verification for the existence of a tropospheric background aerosol having the continents as a source, and they confirm the absence of a significant fractionation of alkali and alkaline earth elements in the production of sea salt. 

Inorganic aerosols near the ocean-atmosphere interface are composed of both salt and dust. The source of the dust is the continents. This is indicated by analyses that show the elements present in proportions close to those found for average crustal rocks. Further evidence is obtained from mineralogical investigation. Dust over the equatorial Atlantic has been found to originate in Africa, and dust in the South Pacific was traced to Australia. Little is known about the chemistry of aerosol dusts over the oceans. Significant changes in the dust component may occur... 

Note that non-acidic sulfate aerosols are produced from sea spray and crustal materials these compounds tend to have larger particle sizes than the typically acidic particles. With the exception of primary emissions of acids, the transformation processes are just as important as the source terms both are needed to produce acid aerosols. Reactions in the aqueous phase (fog) are much faster than in the gas phase and can produce acids on a local scale. The slower gas-phase reactions tend to produce acids on a larger scale, often regional in extent. Organic acids are usually the products of photochemical smog reactions. 

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