Semicontinuous measurements of organic carbon and acidity during the Pittsburgh Air Quality Study: implications for acid-catalyzed organic aerosol formation.

Laboratory evidence suggests that inorganic acid seed particles may increase secondary organic aerosol yields secondary organic aerosol (SOA) through heterogeneous chemistry. Additional laboratory studies, however, report that organic acidity generated in the same photochemical process by which SOA is formed may be sufficient to catalyze these heterogeneous reactions. Understanding the interaction between inorganic acidity and SOA mass is important when evaluating emission controls to meet PM2.5 regulations. We examine semicontinuous measurements of organic carbon (OC), elemental carbon (EC), and inorganic species from the Pittsburgh Air Quality Study to determine if we can detect coupling in the variations of inorganic acidity and OC. We were not able to detect significant enhancements of SOA production due to inorganic acidity in Western Pennsylvania most of the time, but its signal might have been lost in the noise. If we assume a causal relationship between inorganic acidity and OC, reductions in OC for Western Pennsylvania that might result from drastic reductions in inorganic acidity were estimated to be 2 +/- 4% by a regression technique, and an upper bound for this geographic area was estimated to be 5 +/- 8% based on calculations from laboratory measurements.

Mass balance for lead in the California South Coast Air Basin: an update.

A mass balance for lead for the year 1989 in the South Coast Air Basin has inputs to the atmosphere of 600 +/- 190 kg/day and outputs of 580 +/- 160 kg/day, showing rough agreement. Stationary sources are responsible for only about 5% of the total lead emissions. The bulk of the lead is emitted from vehicles using leaded gasoline (37%) and unleaded gasoline (15%), as well as from resuspension of previously deposited lead on roads (43%). Over half of the total emitted lead deposits on roads and nearby soil, while about one-third is carried out the basin by wind. A small amount, less than 10%, is deposited on surfaces throughout the basin. These percentages are approximately the same as those in a mass balance for the same region calculated for 1972, when lead emissions from leaded gasoline were about a factor of 70 greater than leaded gas emissions in 1989. When the lead emissions are used as inputs to a simple continuously stirred flow reactor model for the basin, reasonable agreement is obtained between calculated and measured concentrations.

Behavioral factors affecting exposure potential for household cleaning products.

Behavioral experiments were performed on 342 subjects to determine whether behavior, which could affect the level of personal exposure, is exhibited in response to odors and labels which are commonly used for household chemicals. Potential for exposure was assessed by having subjects perform cleaning tasks presented as a product preference test, and noting the amount of cleaning product used, the time taken to complete the cleaning task, the product preference, and the exhibition of avoidance behavior. Product odor was found to affect product preference in the study with the pleasant odored product being preferred to the neutral and unpleasant products. Product odor was also found to influence the amount of product used; less of the odored products was used compared to the neutral product. The experiment also found that very few of the subjects in the study read the product labels, precluding analysis of the effect of such labels on product use. A postexperiment questionnaire on household cleaning product purchasing and use was administered to participants. The results indicate that significant gender differences exist. Women in the sample reported more frequent purchase and use of cleaning products resulting in an estimated potential exposure 40% greater than for the men in the sample. This finding is somewhat countered by the fact that women more frequently reported exposure avoidance behavior, such as using gloves. Additional significant gender differences were found in the stated importance of product qualities, such as odor and environmental quality. This study suggests the need for further research, in a more realistic use setting, on the impact of public education, labels, and product odor on preference, use, and exposure for different types of consumer products.

Modeling the effects of water usage and co-behavior on inhalation exposures to contaminants volatilized from household water.

The volatilization of volatile organic chemicals during domestic water usage can result in significant indoor air concentrations, and the subsequent inhalation of these contaminants is an important route of exposure. The magnitude of these exposures is highly dependent on the activities undertaken by the exposed individual, as well as the activities of other occupants of the home. The indoor air quality-exposure Model for the Analysis of Volatiles and Residential Indoor Air Quality (MARVIQ) was used to ascertain the impact of water-use activities on the potential contaminant dose to household members. Human time-activity patterns of various population groups were sampled from the California Air Resources Board database, applying distributions of water-use occurrence and water-use duration to each activity based on survey results. Indoor air concentrations in a sample house and the resulting potential inhalation dose to the occupants were computed for different individuals and pairs of individuals to test for exposure and coexposure effects. The simulated daily exposure is well described by a simplified equation that is a function of the amount of time the individual spends in the shower, the bath, and the bathroom; the total water usage in the home; and the fraction of time the individual is at home. These results can be used to identify high-risk populations, individuals, and households. The study also demonstrates the importance of further research on joint time-activity patterns in multiperson households for assessment of exposure and coexposure effects.

Radioactive cesium from the Chernobyl accident in the Greenland Ice Sheet.

Measurements of cesium-134 and cesium-137 in Greenland snow together with models of long-range transport have been used to assess radionuclide deposition in the Arctic after the Chernobyl accident. The results suggest that a well-defined layer of radioactive cesium is now present in polar glaciers, providing a new reference for estimating snow accumulation rates and dating ice core samples.

Sulfate and nitrate concentrations from a South greenland ice core.

An ice core in south Greenland covering the period 1869 to 1984 was analyzed for oxygen isotopes and chloride, nitrate, and sulfate concentrations. The data show that the "excess" (nonsea-salt) sulfate concentration has tripled since approximately 1900 to 1910 and the nitrate concentration has doubled since approximately 1955. The increases may be attributable to the deposition of these chemical specis from air masses carrying North American and Eurasian anthropogenic emissions.

Characterization of airborne trace metal and trace organic species from coal gasification.

Fugitive emissions from a slagging fixed-bed coal-gasification pilot plant were analyzed by flameless atomic absorption spectrophotometry, gas chromatography, and mass spectrometry for trace metal and trace organic species. Analysis of the size distributions of airborne particulate matter inside the plant showed an abundance of large metal-containing particles; outdoor distributions in the vicinity of the plant resembled the indoor distributions, suggesting the importance of the gasifier in influencing ambient air quality. This conclusion was further supported by identification of similar organic compounds inside and outside the plant. Trace element enrichment factors based on the earth's crustal composition were greater than those based on the composition of the lignite used in the gasifier, showing the importance of characterizing the proper source material when inverstigating chemical fraction during aerosol formation. Enrichments in the present study were much greater than those found in previous sampling during aborted start-up and cleaning procedures, where normal operating temperatures had not yet been reached. Both studies showed evidence of enrichment factors which decreased with increasing particle size. Although much of the airborne mass was associated with large particles having low respirability, the high concentrations of some metals indoors suggests that further assessment of potential occupational exposures is warranted.

Characterization of airborne particles at a high-btu coal-gasification pilot plant.

Airborne particles in fugitive emissions have been measured at a slagging fixed-bed coal-gasification pilot plant using lignite. Sampling was conducted during shutdown operations and opening of the gasifier following an aborted startup. Aerosol collected with a Sierra high-volume impactor was subjected to analysis by gas chromatography, mass spectrometry, and scanning electron microscopy; aerosol collected with an Andersen low-volume impactor was subjected to flameless atomic absorption analysis. The data show that the bulk of the trace organic material is associated with small particles: these data are similar to data on ambient air reported in the literature. Particle morphologies resemble those of fly ash from coal combustion, including smooth spheres, vesicular spheres, and crystalline material. Trace element size distributions are bimodal and resemble data for ambient air. Pb-containing particles are generally submicron, while particles containing Al, Fe, and other crustal species are mostly of supermicron size. Aluminum-based aerosol enrichment factors calculated from the lignite composition show that the composition of the aerosol resembles that of the coal, with the exception of modest enrichments of Mg, Na, As, and Pb in the submicron size range. Aerosol enrichment factors based on the earth's crustal composition are somewhat greater than those based on coal composition for several elements, suggesting potential errors in using crustal enrichment data to investigate chemical fractionation during aerosol formation.

Airborne lead and other elements derived from local fires in the himalayas.

The combustion of wood and yak dung for heating and cooking in a populated Nepal Himalayan valley contributes significantly to the ambient airborne concentrations of lead, copper, aluminum, magnesium, and elemental and organic carbon. A comparison of the concentrations of these elements in fresh snow with corresponding values in air suggests that the pollution aerosol is confined to the valley, with pristine air aloft.