Soluble metals in the atmosphere and their biological implications. A study to identify important aerosol components by statistical analysis of PIXE data.

Multivariate statistical analysis has been applied to time series measurements of aerosol elemental composition from PIXE analysis of filter samples, and principal components have been resolved that represent distinct particle types in an external mixture in the atmosphere. In this study, it is argued that a combination of chemical and statistical analyses of the data may be more powerful in determining chemical species in atmospheric aerosols than studied that employ mainly direct chemical analysis of chemical species in unresolved mixtures of aerosol particle samples. Sulfur is generally associated with mineral dust elements. It is reasoned that the association may represent sulfuric acid coatings on particles that can lead to mineral dissolution and solubilization of significant amounts of aluminum, iron, and other metals. Upon wet or dry deposition to the surface, the fluxes of these metals in biologically-available form may be sufficient to affect primary productivity in the world ocean and cause ecological damage in lakes. As a consequence, the fluxes of biogenic trace gases to the atmosphere may be changed, possibly leading to changes in the tropospheric concentration of ozone. The inputs to lakes of soluble aluminum, which is toxic to fish, may be partly by deposition directly from the atmosphere, thus not limited to leaching of soils by acid deposition. Human inhalation of soluble aluminum and other solubilized mineral metals may account, in part, for the observed geographic pattern of deaths attributed to chronic obstructive pulmonary disease (COPD) that show high rates in cities of the Western US and the southeast region, but low in most of the midwest and northeast.

Regional anomalies in chronic obstructive pulmonary disease; comparison with acid air pollution particulate characteristics.

Mortality rates due to chronic obstructive pulmonary disease (COPD) for males and females in standard metropolitan statistical areas are highest in two broad regions of the U.S. One is the southeast, with age-adjusted rates high in Georgia and north Florida but decreasing toward south Florida; the other is the western plains, with rates high in Colorado and north Texas but decreasing toward south Texas. Rates are generally low in the northeast, upper midwest, and far west, as well as in the largest cities of these regions. These geographic patterns suggest that atmospheric environmental conditions may contribute to the risk of COPD. Based on measured aerosol characteristics and atmospheric chemical reasoning, it is argued that ambient air in the high COPD regions may be especially irritating to the respiratory tract because of fine particles that contain the reaction products of acid air pollutants. In the southeast, sulfuric acid aerosol concentrations are high, apparently because of a sunny warm humid climate that favors rapid oxidation of sulfur dioxide as well as the region's proximity to large primary air pollution sources further north. Particulate sulfur is also associated with soil mineral constituents. In the western plains, concentrations of alkaline dust are high because of soil erosion during windy dry conditions. Acid air pollutants can be scavenged to mineral particle surfaces and form chemical reaction products that may include solubilized mineral aluminum. These may be inhaled and deposited in the respiratory tract so as to contribute to COPD mortality risk.

Aerosol lead and associated elements in Beijing, China.

The relative importance of local and regional sources of lead and associated elements in fine and coarse aerosol particles of an urban atmosphere was assessed by means of a two-day study, July 20 and 30, 1980 in Beijing, China. Five near-ground locations were selected for aerosol sampling by cascade impactors and elemental analysis by proton induced X-ray emission (PIXE): the imperial palace courtyard, a park, near two streets, and a mid-street traffic island. These sites, ranked in order of increasing traffic intensity and fugitive surface dust, showed that concentrations of major dust constitutents, represented by coarse particle (>2 µm diameter) Si, Al, and Ca, increased correspondingly. Pb, as well as Zn, As, and Cu, were present mainly in fine (<2 µm) particles; their concentrations were unrelated to traffic, indicating they resulted mainly from regional combustion or other sources. However, these elements also were present in coarse particles at concentrations that varied with the major dust elements and were relatively enriched, compared to average earth crust rock material, by factors of more than 100 (Pb), 50 (Zn), and 10 (Cu). Nonurban Beijing shows much smaller coarse aerosol enrichments of Pb, Zn, and Cu, indicating urban contamination of surface dust. Published data from St. Louis, USA show both fine and coarse aerosol Pb and Zn. Compared with Beijing, fine and coarse concentrations in St. Louis are similar for Pb, but lower for Zn, Ca, and Fe. Both Pb and Zn are enriched relative to earth crust composition to a greater degree in St. Louis than Beijing in both fine and coarse particle size ranges. The results suggest that heavy metals from combustion occur in the air as fine particles and, after deposition on the surface, as reentrained coarse particles of fugitive dust. Both many contribute to human exposures of these heavy metals.

Water-to-Air Fractionation of Bacteria.

Differences in the ability of bacterial species to be transported from water to air by bursting bubbles were investigated. Bubbles were generated in suspensions of mixed bacterial cultures, and the concentration was measured for each species in the top jet drop ejected. This concentration divided by the concentration in the bulk menstruum is the concentration factor (CF). Bubbles were generated 2 cm below the liquid surface, and jet drops with diameters from 34 to 136 mum were studied. Serratia marinorubra and Micrococcus euryhalis had CFs which were generally 10 to 100 times greater than those of Escherichia coli, Pseudomonas bathycetes, and spores of Bacillus subtilis. P. bathycetes never had a CF significantly greater than 1 at any drop size, and spores of B. subtilis had a maximum CF of 4. E. coli had a maximum CF of 6 for 1- or 2-day old cultures, but this increased to 80 when a 5-day-old culture was used. This change in the CF with age of the cells indicates that composition of the cell may be a factor influencing its ability to concentrate in jet drops.

Atmospheric sulfur aerosol concentrations and characteristics from the South american continent.

Aerosol samples collected from eight geographically distinct locations in South America during the austral winter of 1976 and summer of 1977 with six-stage cascade impactors show a tropospheric sulfur background concentration of about 50 nanograms per cubic meter of air in the fine-particle mode (1 micrometer in aerodynamic diameter). Time-sequence filter samples, taken concurrently at most locations, show an average non-sea spray related sulfur concentration of about 85 nanograms per cubic meter. These concentrations are substantially lower than most published nonurban values for the Northern Hemisphere obtained by similar sampling and analysis techniques and may represent a natural tropospheric background level of aerosol sulfur.

Rare earths in hawaiian basalts.

Rare-earth elements have been determined by neutron activation analysis in 20 basalts from the Hawaiian Islands. The abundance patterns of these elements form groups coinciding closely with groupings based on other evidence, and a fractional crystallization mechanism for change in rare earth abundance is implied.