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.     

Controlled Exposures of Volunteers to Respirable Carbon and Sulf uric Acid Aerosols

Respirable carbon or fly ash particles are suspected to increase the respiratory toxicity of coexisting acidic air pollutants, by concentrating acid on their surfaces and so delivering it efficiently to the lower respiratory tract. To investigate this issue, we exposed 15 healthy and 15 asthmatic volunteers in a controlled- environment chamber (21°C, 50 percent relative humidity) to four test atmospheres: (i) clean air; (ii) 0.5-μm H2SO4 aerosol at =100 μg/m³, generated from water solution; (iii) 0,5-μm carbon aerosol at =250 μg/m³, generated from highly pure carbon black with specific surface area comparable to ambient pollution particles; and (iv) carbon as in (iii) plus =100 μg/m³ of ultrafine H2SO4 aerosol generated from fuming sulfuric acid. Electron microscopy showed that nearly all acid in (iv) became attached to carbon particle surfaces, and that most particles remained in the sub-μm size range. Exposures were performed double-blind, 1 week apart. They lasted 1 hr each, with alternate 10-min periods of heavy exercise (ventilation =50 L/min) and rest. Subjects gargled citrus juice before exposure to suppress airway ammonia. Lung function and symptoms were measured pre-exposure, after initial exercise, and at endexposure. Bronchial reactivity to methacholine was measured after exposure. Statistical analyses tested for effects of H₂SO₄ or carbon, separate or interactive, on health measures. Group data showed no more than small equivocal effects of any exposure on any health measure. One individual's responses were consistent with a clinically significant excess airway constriction from H₂SO₄ plus carbon, and 2-3 others showed slight excess responses to the combined pollutants, but all these observations might have reflected chance variations. We conclude that coexisting carbon aerosol did not increase respiratory irritancy of H₂SO₄, in most healthy and asthmatic subjects exposed for 1 hr under simulated "worst-case" ambient conditions.     

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.     

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].     

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.     

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.     

Forecasting Air Pollution Potential: A Synoptic Climatological Approach

ABSTRACT

This paper describes the development and application of an air pollution potential (APP) forecast model based on a synoptic climatological approach in a heavily industrialized area in Durban, South Africa. The aim of the forecasting procedure, based on a system of orange, red, and all-clear alerts, was to give industry advance warning of periods of poor atmospheric dispersion so that it could take action to reduce emissions. The key meteorological parameter in accurately identifying the commencement of an APP episode was found to be negative surface pressure tendency. Wind direction was the most useful parameter in estimating the end point of an APP episode. The model was very successful in identifying periods of elevated SO₂, but there is a need for further refinement in forecasting the end point of an episode.     

Pilot-Scale Demonstration of an Innovative Treatment for Vapor Emissions

ABSTRACT

Researchers from the National Renewable Energy Laboratory recently conducted a pilot-scale study at McClellan Air Force Base (AFB) in Sacramento, CA. The objective of the test was to determine the effectiveness of an ambient-temperature, solar-powered photocatalytic oxidation treatment unit for destroying emissions of chlorinated organic compounds from an air stripper. This paper reports test results and discusses applications and limitations of the technology.

A 10-standard-cubic-foot-per-minute (SCFM) (28.3 L/min) slip stream of air from an air stripper at Operative Unit 29-31 at McClellan AFB was passed through a reactor that contained a lightweight, perforated, inert support coated with photoactive titanium dioxide. The reactor faced south and was tilted at a 45° angle from vertical so that the light-activated catalyst received most of the available sunlight. An online portable gas chro-matograph with two identical columns simultaneously analyzed the volatile organic compounds contained in the reactor inlet and outlet air streams. Summa canister grab samples of the inlet and outlet were also collected and sent to a certified laboratory for U.S. Environmental

Protection Agency Method TO-14 analysis and verification of our field analyses. Three weeks of testing demonstrated that the treatment system's destruction and removal efficiencies (DREs) are greater than 95% at 10 SCFM with UV intensities at or greater than 1.5 milliwatts/square centimeter (mW/cm²). DREs greater than 95% at 20 SCFM were obtained under conditions where UV irradiation measured at or greater than 2 mW/cm². In Sacramento, this provided 6 hours of operation per clear or nearly clear day in April. A solar tracking system could extend operating time. The air stream also contained trace amounts of benzene. We observed no loss of system performance during testing.