Measurement of Toxic and Related Air Pollutants

A joint conference for the fifth straight year cosponsored by the Air & Waste Management Association’s EM-3, EM-4, and ITF-2 technical committees, and the Atmospheric Research and Exposure Assessment Laboratory (AREAL) of the U.S. Environmental Protection Agency, was held in Raleigh, North Carolina, May 1–4, 1990. The technical program consisted of 187 presentations, held in 20 technical sessions, on recent advances in the measurement and monitoring of toxic and related pollutants found in ambient and source atmospheres. Covering a wide range of measurement topics and supported by 66 exhibitors of instrumentation and consulting services, the symposium was attended by more than 850 professionals from the United States and other countries. This overview highlights a selection of the technical presentations. A synopsis of the keynote address to the symposium is also included.     

The Regulation of Toxic Air Pollutants A Critical Review

ABSTRACT

Passage of the 1990 Clean Air Act Amendments launched the Acid Rain Program in the United States. This initiative, based on the market mechanism of a sulfur dioxide tradable “allowance” system, was a dramatic departure from traditional command and control strategies designed to reduce air pollution emissions. Power plant managers have flexibility under the program to select and implement a variety of options to reduce emissions below mandated levels. Federal agencies have collected annual performance data for affected facilities covered by the program for a number of years. Coal-burning plants are typically greater generators of sulfur dioxide (SO₂) than oil burners of equivalent size. This study examined the effect of fuel type as a significant factor influencing a plant's achievement in reducing pollution emissions. Achievement was measured by using a derived variable, delta (A), defined as the difference between pounds of SO₂ produced divided by the energy (in million Btu) generated, for the years 1990 and 1995. Rigorous nonparametric statistical analyses were used to compare the two populations of coal-fired and oil-fired plants. Results indicated that coal-burning facilities achieved greater program success, measured by the expected value of delta, than the oil combustors for the five-year period reviewed. Since utility managers must take steps to ensure all applicable requirements of the program are met, findings of the inquiry should prove to be useful in assessing achievable emissions reductions and aid in long-range facility planning.     

A Regujatory Framework for Setting Air Emission Limits for Noncriteria Pollutants

The information presented in this paper is concerned with the effects of ambient ozone on crop yield reduction and the resultant economic losses. Yield data for nine crops within the South Coast Air Basin (SCAB) of California were obtained for the 12-year period, 1964 through 1975. Ozone concentrations, temperature, precipitation, and relative humidity data were related to the yields by using regression models. Estimated yield reductions due to ozone for 1975, varied from zero to 57% depending on crop and location. Economic welfare losses calculated from the yield reductions were $57.3 and $45.7 million for producer’s and consumer’s surplus, respectively. The total loss from ozone to agriculture related economic sectors determined by input-output analysis was $276 million in the SCAB and $36.6 million in the remainder of the state.     

Flexibility of X-Ray Emission Spectrography as Adapted to Microanalysis of Air Pollutants

Methods previously published by this laboratory for analyzing thin dust coatings of airborne particulates have been further evaluated, as applied to vast air pollution surveys. It was demonstrated that choice of glass fiber filters adapted to high-volume samplers restricts the analysis to a limited number of elements, such as lead. More flexibility and versatility are attained through the use of organic membrane filters mounted in small plastic monitors which permit multi-elemental analysis at least as accurately as with other popular but time-consuming techniques. These qualities of speed and accuracy allow shorter intervals of sampling which are normally required for better statistical assessment of broad air pollution surveys. Sensitivity of the technique reaches a value close to 0.05 μg/m³, while time of analysis required is about five minutes per element after receipt of the sample.     

Evaluation of the Effects of Emission Reductions on Secondary Particulate Matter in the South Coast Air Basin of California

An Aerosol Trajectory Model (ATM) is applied to the South Coast Air Basin of California for a two-day episode in August 1982 to evaluate proposed control strategies that aim to reduce atmospheric aerosols. Model predictions Indicate that secondary organic aerosols decrease linearly with reactive hydrocarbon emissions. In addition, the model shows that If sulf ate is produced only in the gas phase by oxidation of SO₂, then reduction In SO₂ emissions yields a nearly proportional decrease In sulfate levels. Reduction in ammonia emissions, combined with reduction of NO_x emissions, gives the best results In terms of nitrate control. The order in which the emission controls are implemented Is predicted to have a major impact on the reduction of secondary atmospheric aerosols.     

Summary of the 1991 EPA/A&WMA International Symposium: Measurement of Toxic and Related Air Pollutants

A joint conference cosponsored for the sixth year by the Atmospheric Research and Exposure Assessment Laboratory (AREAL) of the U.S. Environmental Protection Agency and the Air & Waste Management Association was held in Durham, North Carolina, May 6–10, 1991. The technical program consisted of 220 presentations, held in 25 technical sessions, on recent advances in ambient and source atmospheres. Covering a wide range of measurement topics and supported by 78 exhibitors of instrumentation and consulting services, the symposium was attended by almost a thousand professionals from the United States and other countries. This overview highlights a selection of the technical presentations, and includes a synopsis of the keynote address.     

Summary of the 1989 EPA/A&WMA International Symposium: Measurement of Toxic and Related Air Pollutants

A joint conference, for the fourth straight year cosponsored by the Air & Waste Management Association’s TP-6, TP-7, and ITF-2 technical committees, and the Atmospheric Research and Exposure Assessment Laboratory of the U. S. Environmental Protection Agency, was held at Raleigh, North Carolina, May 2-5, 1989. The technical program consisted of 145 presentations, held in 14 separate technical sessions, on recent advances in the measurement and monitoring of toxic and related pollutants found in ambient and source atmospheres. Covering a wide range of measurement topics and superbly supported by 57 exhibitors of instrumentation and consulting services, the symposium was enthusiastically received by more than 700 attendees from the United States and other countries. This overview contains a selection of the highlights from the technical presentations. A synopsis of the keynote address to the symposium is also included.     

Outdoor-Indoor Levels of Six Air Pollutants

Comparisons were made of the levels of six air pollutants—total oxidant, per-oxyacetyl nitrate (PAN), nitric oxide, nitrogen dioxide, carbon monoxide, and particulate matter—outside and inside 11 buildings in the South Coast Basin of California during summer and fall.

Total oxidant levels inside depend upon how much outside air is being brought in and the residence time in the structure. With rapid intake and circulation, levels inside may be two-thirds those outside. With little intake and slow circulation, amounts inside decay to near zero. PAN is more persistent in buildings because it is more stable than ozone but also decays to low levels over an extended period. Oxides of nitrogen and CO are much more stable than oxidant or PAN and when carried into buildings remain until diluted or exhausted.

Particulate matter levels indoors depend largely upon velocity of air movement. Indoor areas where foot traffic was light or which had low ventilation rates had reduced amounts of particulate. Electrostatic precipitators were much more effective than coarse primary filters used in many buildings for removing particulate matter.     

Codependencies of reactive air toxic and criteria pollutants on emission reductions

It is important to understand the effects of emission controls on concentrations of ozone, fine particulate matter (PM2.5), and hazardous air pollutants (HAPs) simultaneously, to evaluate the full range of health, ecosystem, and economic effects. Until recently, the capability to simultaneously evaluate interrelated atmospheric pollutants ("one atmosphere" analysis) was unavailable to air quality managers. In this work, we use an air quality model to examine the potential effect of three emission reductions on concentrations of ozone, PM2.5, and four important HAPs (formaldehyde, acetaldehyde, acrolein, and benzene) over a domain centered on Philadelphia for 12-day episodes in July and January 2001. Although NO(x) controls are predicted to benefit PM2.5 concentrations and sometimes benefit ozone, they have only a small effect on formaldehyde, slightly increase acetaldehyde and acrolein, and have no effect on benzene in the July episode. Concentrations of all pollutants except benzene increase slightly with NO(x) controls in the January simulation. Volatile organic compound controls alone are found to have a small effect on ozone and PM2.5, a less than linear effect on decreasing aldehydes, and an approximately linear effect on acrolein and benzene in summer, but a slightly larger than linear effect on aldehydes and acrolein in winter. These simulations indicate the difficulty in assessing how toxic air pollutants might respond to emission reductions aimed at decreasing criteria pollutants such as ozone and PM2.5.     

Formation and Removal Reactions of Hazardous Air Pollutants

Current regulatory policies for hazardous air pollutants (HAPs) target the sources of direct emissions. In addition to direct emissions, some of the aromatic, nitrogenated, and oxygenated HAPs can be formed in the atmosphere. Formaldehyde and acetaldehyde, in particular, are produced by almost every hydrocarbon photooxidation reaction. Estimates have been made that, in some urban areas, in situ formation contributes as much as 85 percent of the ambient levels of formaldehyde and 95 percent for acetaldehyde. Over 40 percent of the HAPs being regulated under Title III of the 1990 Clean Air Act Amendments have atmospheric lifetimes of less than one day. The transformation products of these HAPs with low atmospheric persistence are important for assessing risks to human health, especially for cases where the transformation products are more toxic than the HAP itself.     

Potential Impact on Standards for Toxic Air Contaminants

Since the Bhopal incident, the public has placed pressure on regulatory agencies to set community exposure limits for the dozens of chemicals that may be released by manufacturing facilities. More or less objective limits can be established for the vast majority of these chemicals through the use of risk assessment. However, each step of the risk assessment process (i.e., hazard identification, dose-response assessment, exposure assessment, and risk characterization) contains a number of pitfalls that scientists need to avoid to ensure that valid limits are established. For example, in the hazard identification step there has been little discrimination among animal carcinogens with respect to mechanism of action or the epidemiology experience. In the dose-response portion, rarely is the range of “plausible” estimated risks presented. Physiologically based pharmacokinetic (PB-PK) models should be used to understand the difference between the tissue doses and the administered dose, as well as the difference in target tissue concentrations of the toxicant between rodents and humans. Biologically-based models like the Moolgavkar-Knudson-Venzon (MKV) should be developed and used, when appropriate. The exposure assessment step can be significantly improved by using more sensitive and specific sampling and analytical methods, more accurate exposure parameters, and computer models that can account for complex environmental factors. Whenever possible, model predictions of exposure and uptake should be validated by biological monitoring of exposed persons (urine, blood, adipose) or by field measurements of plants, soil, fish, air, or water. In each portion of an assessment, the weight of evidence approach should be used to identify the most defensible value. In the risk characterization, the best estimate of the potential risk as well as the highest plausible risk should be presented. Future assessments would be much improved if quantitative uncertainty analyses were conducted. Procedures are currently available for making future assessments. By correcting some of these shortcomings in how health risk assessments have been conducted, scientists and risk managers should be better able to identify scientifically appropriate ambient air standards and emission limits.     

Report from the Symposium on Air Quality Criteria

Neither time nor space permitted full reporting of the Symposium on Air Quality Criteria, held June 4-5, 1968, in New York City. The Symposium was sponsored by the Air Pollution Control Association, the American Industrial Hygiene Association, the American Petroleum Institute, and the Industrial Medical Association and its educational affiliate, The Occupational Health Institute.

Published here are excerpts from, or author’s abstracts of, the eight principal papers presented at the Symposium.

Not included are the prepared discussions which followed the delivery of the papers.

A full proceedings, including prepared discussions, general discussions, and summation, will be published in the September issue of the Journal of Occupational Medicine, 55 E. Washington Street, Chicago, Illinois 60602.     

A Method for Predicting the Performance of Packed Columns Operating with a Reactive Scrubbing Liquid That Control Gaseous Air Pollutants

Abstract

A method for predicting the performance of packed columns that control gaseous air pollutants has been developed that exploits the advances in both computer software and hardware commonly used by practicing engineers. The solution of the simultaneous partial differential equations that describe the absorption process in packed columns that occurs in the presence of chemical reaction is obtained by converting the partial differential equations to systems of ordinary differential equations. These systems of ordinary differential equations are then solved using the method of lines along with a variable step, variable order numerical method. The method is applicable to systems in which there are multiple reactions within the liquid phase. The reactions can be of any order and can be reversible. The programming is simple and the machine running time is minimal. The method is illustrated here with an example.     

Optimization of Height of Release of Air Pollutants

A number of key projects in the Environmental Protection Agency (EPA) particulate R&;D program having applicability to industry are presented. For electrostatic precipitators (ESP) there is presented the result of work on large diameter discharge electrodes which provide a decrease in penetration of up to a factor of 4 when compared to conventional small diameter electrodes. Also discussed is the multistage ESP which provides a collection efficiency that would require a collecting plate area 4 or 5 times larger with conventional ESP technology. The E-SOX technology makes use of the multistage concept to free up space in the ESP for SO₂ removals of up to 90%. Electrostatically augmented fabric filtration provides a reduction in pressure drop of about 5 0% as compared to conventional fabric filtration. Wind tunnel modeling of windbreaks for material storage piles indicates a potential for providing engineering design data that would allow significant emission reduction caused by wind erosion     

Collaborative Testing of Methods to Measure Air Pollutants

A collaborative test was conducted to determine the precision of the chemiluminescent method which has been specified for measuring ozone, to determine photochemical oxidant. Ten laboratories participated in a test involving the analysis of an urban atmosphere containing a photochemical smog mixture. Ozone generators were used to increase the O₃ level over that naturally occurring, in order to cover an adequate range of concentrations. The range tested was 0 to 0.5 ppm.

A statistical analysis of the data obtained was used to derive equations for within laboratory and between laboratory standard deviations. In order to evaluate sampling data, these equations can be used in various statistical procedures to estimate repeatability, reproducibility, lower detectable limit, and other measures that establish the precision of the method.

Using specific definitions for repeatability and reproducibility, the following approximate estimates were obtained in the range of zero to 0.5 ppm:

Repeatability—0.01 to 0.04 ppm (varies with concentration, linear).

Reproducibility—0.01 to 0.09 ppm (varies with concentration, non-linear).

The lower detectable limit depends on instrumental and other variables, and cannot be specified precisely. Under typical assumptions, this limit can be estimated at between 0.006 and 0.009 ppm.     

Standardization of Methods For Measurement of Air Pollutants

Currently available compilations of methods of air analysis are listed. Collaborative testing is urgently needed to reconcile differences and to demonstrate the accuracy of these methods. The Analytical Methods Evaluation Service of the National Center for Air Pollution Control conducted a survey of the instruments and manual methods of analysis in use. Responses are tabulated from about 80 laboratories, in 28 states and 3 foreign countries. Sulfur dioxide was the most widely measured pollutant. The first collaborative study organized by the Analytical Methods Evaluation Service is described. The purpose was to evaluate the permeation tube technique as a primary standard method for generating known sulfur dioxide concentrations for instrument calibration and methods testing. Although a good beginning has been made, the testing of methods for measuring air pollutants has barely begun.     

Fading of Selected Drapery Fabrics by Air Pollutants

A statistically designed laboratory study to assess both direct and synergistic effects of air pollutants and other environmental factors on six different classes of materials was recently completed.¹ One of the material classes was dyed textile fabrics. Drapery fabrics were specifically selected because they are economically important, are designed to have a fairly long life, and are subject to atmospheric fading. In fact, fading, whether caused by sunlight, pollution or both, frequently limits the useful life of draperies.