Reactivity-Based Hydrocarbon Controls: Scientific Issues and Potential Regulatory Applications

The California Air Resources Board and the South Coast Air Quality Management District hosted a conference on April 8-9, 1991 to examine the scientific issues associated with reactivity-based hydrocarbon controls, and to identify the obstacles to potential regulatory applications. Owing to residual uncertainties in the underlying science, and the complex emission measurement capabilities required for enforcement, a general consensus emerged on the need for further research before application of reactivity-based controls. A number of recommendations were made for research on the remaining scientific, enforcement, and policy issues, many of which have led to cooperative efforts initiated since the conference.     

Wind Tunnel Modelling of Roadways: Comparison with Mathematical Models

The assessment of air quality impacts from roadways is a major concern to urban planners. In order to assess future road and building configurations, a number of techniques have been developed, including mathematical models, which simulate traffic emissions and atmospheric dispersion through a series of mathematical relationships and physical models. The latter models simulate emissions and dispersion through scaling of these processes in a wind tunnel. Two roadway mathematical models, HIWAY-2 and CALINE-4, were applied to a proposed development in a large urban area. Physical modelling procedures developed by Rowan Williams Davies & Irwin Inc. (RWDI) in the form of line source simulators were also applied, and the resulting carbon monoxide concentrations were compared. The results indicated a factor of two agreement between the mathematical and physical models. The physical model, however, reacted to changes in building massing and configuration. The mathematical models did not, since no provision for such changes was included in the mathematical models. In general, the RWDI model resulted in higher concentrations than either HIWAY-2 or CALINE-4. Where there was underprediction, it was often due to shielding of the receptor by surrounding buildings. Comparison of these three models with the CALTRANS Tracer Dispersion Experiment showed good results although concentrations were consistently underpredicted.     

Low Concentration Mercury Sorption Mechanisms and Control by Calcium-Based Sorbents: Application in Coal-Fired Processes

ABSTRACT

The capture of elemental mercury (Hg⁰) and mercuric chloride (HgCl₂) by three types of calcium (Ca)-based sor-bents was examined in this bench-scale study under conditions prevalent in coal-fired utilities. Ca-based sorbent performances were compared with that of an activated carbon. Hg⁰ capture of about 40% (nearly half that of the activated carbon) was achieved by two of the Ca-based sorbents. The presence of sulfur dioxide (SO₂) in the simulated coal combustion flue gas enhanced the Hg⁰ capture from about 10 to 40%. Increasing the temperature in the range of 65-100 °C also caused an increase in the Hg⁰ capture by the two Ca-based sorbents. Mercuric chloride (HgCl₂) capture exhibited a totally different pattern. The presence of SO₂ inhibited the HgCl₂ capture by Ca-based sorbents from about 25 to less than 10%. Increasing the temperature in the studied range also caused a decrease in HgCl₂ capture. Upon further pilot-scale confirmations, the results obtained in this bench-scale study can be used to design and manufacture more cost-effective mercury sorbents to replace conventional sorbents already in use in mercury control.     

Comparative Study of Spray Booth Filter System Efficiency

ABSTRACT

During recent years, greater emphasis has been placed on the control of particulate emissions from painting operations. This has gained more importance as more is learned about the potential release of toxic metals to the atmosphere from painting operations. This has led to queries about the efficiency of various painting arrestor systems to reduce particulate discharges to the atmosphere. Even more important is the capability of the arrestor systems to control PM₁₀ emissions.

In 1995, the U.S. Environmental Protection Agency initiated a study to evaluate various dry paint overspray arrestor systems. This study was designed to evaluate not only the total emissions control capability of the arrestor but also the PM₁₀ control capability of the various system designs. Paint overspray arrestor systems using five different filtration concepts or materials were selected. They include systems constructed of fiberglass, paper, Styrofoam, and cardboard materials. These systems used filtration techniques incorporating the following filtration phenomena and designs: cyclone, baffle, bag systems, and mesh systems.

The testing used an optical particle counting procedure to determine the concentration of particles of a given size fraction to penetrate a test arrestor system. The results of the testing indicated that there are significant differences in the efficiency of the tested system designs to capture and retain PM₁₀.

This paper summarizes the results of the research conducted to determine the capability of the arrestor systems to capture particulate of sizes down to approximately 1 μm in surface diameter.     

Seasonal Variations in Aerosol Composition and Acidity at Shenandoah and Great Smoky Mountains National Parks

The concentration of elements Na through Pb, select ions, and organic carbon from fine (<2.5 µm) particles has been monitored at Shenandoah and Great Smoky Mountains National Parks from 1988 through 1995. The data obtained from 1988 through 1994 show that significant changes in the concentrations of many aerosol constituents occur on a seasonal basis. Particulate sulfate and organic carbon are shown to exhibit substantially higher concentrations during the summer, while sulfur dioxide and nitrate concentrations are highest during the winter.

A method for estimating the degree of neutralization of particulate sulfate is given. This method uses routinely measured aerosol elemental compositions because ammonium ion, the primary neutralizing species for sulfate, is not measured on a routine basis. Application of this method to the selected data set shows that sulfate aerosol is most acidic during summer with an average molar H_s (moles of hydrogen associated with sulfur) to S (moles of sulfur) ratio of approximately 4. This suggests the average sulfate particle during the summer has a molar coon slightly more acidic than ammonium bisulfate (NH₄HSO₄) which has a molar hydrogen to sulfur ratio of 5. Winter H_s to S ratios, however, are approximately 8, suggesting the aerosol is on average fully neutralized ammonium sulfate [(NH₄)₂SO₄].     

Statistical Considerations in Determining the Health Significance of Constituents of Airborne Particulate Matter

ABSTRACT

Because of the U.S. Environmental Protection Agency’s (EPA) new ambient air quality standard for fine particles, the need is likely to continue for more detailed scientific investigation of various types of particles and their effects on human health. Epidemiology studies have become the method of choice for investigating health responses to such particles and to other air pollutants in community settings. Health effects have been associated with virtually all of the gaseous criteria pollutants and with the major constituents of airborne particulate matter (PM), including all size fractions less than about 20 gm, inorganic ions, carbonaceous particles, metals, crustal material, and biological aerosols. In many of the more recent studies, multiple pollutants or agents (including weather variables) have been significantly associated with health responses, and various methods have been used to suggest which ones might be the most important. In an ideal situation, classical least-squares regression methods are capable of performing this task. However, in the real world, where most of the pollutants are correlated with one another and have varying degrees of measurement precision and accuracy, such regression results can be misleading. This paper presents some guidelines for dealing with such collinearity and model comparison problems in both single- and multiple-pollutant regressions. These techniques rely on mean effect (attributable risk) rather than statistical significance per se as the preferred indicator of importance for the pollution variables.     

Characterization of Fine Particulate Matter Produced by Combustion of Residual Fuel Oil

ABSTRACT

Combustion experiments were carried out on four different residual fuel oils in a 732-kW boiler. PM emission samples were separated aerodynamically by a cyclone into fractions that were nominally less than and greater than 2.5 |j.m in diameter. However, examination of several of the samples by computer-controlled scanning electron microscopy (CCSEM) revealed that part of the PM_2.5 fraction consists of carbonaceous cenospheres and vesicular particles that range up to 10 |j.m in diameter. X-ray absorption fine structure (XAFS) spectroscopy data were obtained at the S, V, Ni, Fe, Cu, Zn, and As K-edges and at the Pb L-edge. Deconvolution of the X-ray absorption near edge structure (XANES) region of the S spectra established that the dominant molecular forms of S present were sulfate (26-84% of total S) and thiophene (13-39% of total S). Sulfate was greater in the PM_2.5 samples than in the PM₂₅₊ samples. Inorganic sulfides and elemental sulfur were present in lower percentages. The Ni XANES spectra from all of the samples agreed fairly well with that of NiSO₄, while most of the V spectra closely resembled that of vanadyl sulfate (VO?SO₄?xH₂O). The other metals investigated (i.e., Fe, Cu, Zn, and Pb) also were present predominantly as sulfates. Arsenic was present as an arsen-ate (As⁺⁵). X-ray diffraction patterns of the PM_2.5 fraction exhibit sharp lines due to sulfate compounds (Zn, V, Ni, Ca, etc.) superimposed on broad peaks due to amorphous carbons. All of the samples contain a significant organic component, with the loss on ignition (LOI) ranging from 64 to 87% for the PM_2.5 fraction and from 88 to 97% for the PM_2.5+ fraction. Based on ¹³C nuclear magnetic resonance (NMR) analysis, the carbon is predominantly condensed in graphitic structures. Aliphatic structure was detected in only one of seven samples examined.     

Daily Mortality in the Philadelphia Metropolitan Area and Size-Classified Particulate Matter

ABSTRACT

Time-series of daily mortality data from May 1992 to September 1995 for various portions of the seven-county Philadelphia, PA, metropolitan area were analyzed in relation to weather and a variety of ambient air quality parameters. The air quality data included measurements of size-classified PM, SO₄ ^2-, and H+ that had been collected by the Harvard School of Public Health, as well as routine air pollution monitoring data. Because the various pollutants of interest were measured at different locations within the metropolitan area, it was necessary to test for spatial sensitivity by comparing results for different combinations of locations. Estimates are presented for single pollutants and for multiple-pollutant models, including gaseous pollutants and mutually exclusive components of PM (PM_2.5 and coarse particles, SO₄ ^2- and non-SO₄ ^2- portions of total suspended particulate [TSP] and PM₁₀), measured on the day of death and the previous day.

We concluded that associations between air quality and mortality were not limited to data collected in the same part of the metropolitan area; that is, mortality for one part may be associated with air quality data from another, not necessarily neighboring, part. Significant associations were found for a wide variety of gaseous and particulate pollutants, especially for peak O₃. Using joint regressions on peak O₃ with various other pollutants, we found that the combined responses were insensitive to the specific other pollutant selected. We saw no systematic differences according to particle size or chemistry. In general, the associations between daily mortality and air pollution depended on the pollutant or the PM metric, the type of collection filter used, and the location of sampling. Although peak O₃ seemed to exhibit the most consistent mortality responses, this finding should be confirmed by analyzing separate seasons and other time periods.