Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

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.     

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.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

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.