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Rethinking the Ozone
Problem in Urban and
Regional Air Pollution

Committee on Tropospheric Ozone Formation and Measurement
Board on Environmental Studies and Toxicology
Board on Atmospheric Sciences and Climate
Commission on Geosciences, Environment, and Resources
National Research Council

NATIONAL ACADEMY PRESS
Washington, D.C. 1991

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National Academy Press2101 Constitution Ave., N.W. Washington, D.C. 20418
NOTICE: The project that is the subject of this report was approved by the Governing Board of the

National Research Council, whose members are drawn from the councils of the National Academy
of Sciences, the National Academy of Engineering, and the Institute of Medicine. The members of
the committee responsible for the report were chosen for their special competencies and with regard
for appropriate balance.
This report has been reviewed by a group other than the authors according to procedures
approved by a Report Review Committee consisting of members of the National Academy of Sciences, the National Academy of Engineering, and the Institute of Medicine.
The National Academy of Sciences is a private, nonprofit, self-perpetuating society of distinguished scholars engaged in scientific and engineering research, dedicated to the furtherance of
science and technology and to their use for the general welfare. Upon the authority of the charter
granted to it by the Congress in 1863, the Academy has a mandate that requires it to advise the federal government on scientific and technical matters. Dr. Frank Press is president of the National
Academy of Sciences.
The National Academy of Engineering was established in 1964, under the charter of the
National Academy of Sciences, as a parallel organization of outstanding engineers. It is autonomous
in its administration and in the selection of its members, sharing with the National Academy of Sciences the responsibility for advising the federal government. The National Academy of Engineering
also sponsors engineering programs aimed at meeting national needs, encourages education and
research, and recognizes the superior achievements of engineers. Dr. Robert M. White is president
of the National Academy of Engineering.
The Institute of Medicine was established in 1970 by the National Academy of Sciences to
secure the services of eminent members of appropriate professions in the examination of policy matters pertaining to the health of the public. The Institute acts under the responsibility given to the
National Academy of Sciences by its congressional charter to be an adviser to the federal government and, upon its own initiative, to identify issues of medical care, research, and education. Dr.
Stuart Bondurant is acting president of the Institute of Medicine.
The National Research Council was organized by the National Academy of Sciences in 1916 to
associate the broad community of science and technology with the Academy's purposes of furthering knowledge and advising the federal government. Functioning in accordance with general policies determined by the Academy, the Council has become the principal operating agency of both the
National Academy of Sciences and the National Academy of Engineering in providing services to
the government, the public, and the scientific and engineering communities. The Council is administered jointly by both Academies and the Institute of Medicine. Dr. Frank Press and Dr. Robert M.
White are chairman and vice chairman, respectively, of the National Research Council.
The project was supported by the American Petroleum Institute, the Department of Energy
grant No. DE-FG001-89FE61873, the Environmental Protection Agency grant No. CR-816174-01,
and the Motor Vehicle Manufacture Association of the United States.
Librar y of Congress Catalog. No 91-68142
International Standard Book Numbe r 0-309-04631-9

This book is printed on acid-free recycled stock.
Copyright ©1992 by the National Academy of Sciences.
Cover photo: M. Cerone/Superstock, Inc.
Printed in the United States of America
First Printing, January 1992
Second Printing, March 1994

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Committee on Tropospheric Ozone Formation and
Measurement
JOHN H. SEINFELD (Chairman), California Institute of Technology, Pasadena
ROGER ATKINSON, University of California, Riverside
RONALD L. BERGLUND, Brown and Root, Inc., Houston Texas
WILLIAM L. CHAMEIDES, Georgia Institute of Technology, Atlanta
WILLIAM R. COTTON, Colorado State University, Fort Collins
KENNETH L. DEMERJIAN, State University of New York, Albany
JOHN C. ELSTON, New Jersey Department of Environmental Protection,
Trenton
FRED FEHSENFELD, National Oceanic and Atmospheric Administration,
Boulder
BARBARA J. FINLAYSON-PITTS, California State University, Fullerton

ROBERT C. HARRISS, University of New Hampshire, Durham
CHARLES E. KOLB, JR., Aerodyne Research, Inc., Billerica, Massachusetts
PAUL J. LIOY, University of Medicine and Dentistry of New Jersey-Robert
Wood Johnson Medical School, Piscataway, New Jersey
JENNIFER A. LOGAN, Harvard University, Cambridge, Massachusetts
MICHAEL J. PRATHER, NASA/Goddard Institute for Space Studies, New
York, New York
ARMISTEAD RUSSELL, Carnegie-Mellon University, Pittsburgh
BERNARD STEIGERWALD (Deceased, November 5, 1989)
Project Staff
RAYMOND A. WASSEL, Project Director
ROBERT B. SMYTHE, Senior Staff Officer
WILLIAM H. LIPSCOMB, Research Assistant
KATE KELLY, Editor
ANNE SPRAGUE, Information Specialist
FELITA S. BUCKNER, Project Assistant

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Board on Environmental Studies and Toxicology
PAUL G. RISSER (Chairman), University of New Mexico, Albuquerque
GILBERT S. OMENN (Immediate Past Chairman), University of Washington,

Seattle
FREDERICK R. ANDERSON, Washington School of Law, American University
JOHN C. BAILAR, III, McGill University School of Medicine, Montreal
LAWRENCE W. BARNTHOUSE, Oak Ridge National Laboratory, Oak Ridge
GARRY D. BREWER, Yale University, New Haven
EDWIN H. CLARK, Department of Natural Resources & Environmental
Control, State of Delaware, Dover
YORAM COHEN, University of California, Los Angeles
JOHN L. EMMERSON, Lilly Research Laboratories, Greenfield, Indiana
ROBERT L. HARNESS, Monsanto Agricultural Company, St. Louis
ALFRED G. KNUDSON, Fox Chase Cancer Center, Philadelphia
GENE E. LIKENS, The New York Botanical Garden, Millbrook
PAUL J. LIOY, UMDNJ-Robert Wood Johnson Medical School, Piscataway,
New Jersey
JANE LUBCHENCO, Oregon State University, Corvallis
DONALD MATTISON, University of Pittsburgh, Pittsburgh
GORDON ORIANS, University of Washington, Seattle
NATHANIEL REED, Hobe Sound, Florida
MARGARET M. SEMINARIO, AFL/CIO, Washington, DC
I. GLENN SIPES, University of Arizona, Tucson
WALTER J. WEBER, JR., University of Michigan, Ann Arbor
Staff
JAMES J. REISA, Director
DAVID J. POLICANSKY, Associate Director and Program Director for
Applied Ecology and Natural Resources
RICHARD D. THOMAS, Associate Director and Program Director for Human
Toxicology and Risk Assessment
LEE R. PAULSON, Program Director for Information Systems and Statistics
RAYMOND A. WASSEL, Program Director for Environmental Sciences and
Engineering

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Board on Atmospheric Sciences and Climate
JOHN A. DUTTON (Chairman), Pennsylvania State University
JON F. BARTHOLIC, Michigan State University
E. ANN BERMAN, Tri-Space, Inc.
RAFAEL L. BRAS, Massachusetts Institute of Technology
MOUSTAFA T. CHAHINE, California Institute of Technology
ROBERT A. DUCE, University of Rhode Island
THOMAS E. GRAEDEL, AT&T Bell Laboratories
DAVID D. HOUGHTON, University of Wisconsin, Madison
EUGENIA KALNAY, National Oceanic and Atmospheric Administration
RICHARD S. LINDZEN, Massachusetts Institute of Technology
SYUKURO MANABE, National Oceanic and Atmospheric Administration
GERALD R. NORTH, Texas A&M University
JAMES J. O'BRIEN, Florida State University
JOANNE SIMPSON, National Aeronautics and Space Administration
Ex-Officio Members
ERIC J. BARRON, Pennsylvania State University
PETER V. HOBBS, University of Washington
CHARLES E. KOLB, Aerodyne Research, Inc.

DONALD J. WILLIAMS, The Johns Hopkins University
Staff
WILLIAM A. SPRIGG, Staff Director

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Commission on Geosciences, Environment, and Resources
M. GORDON WOLMAN (Chairman), The Johns Hopkins University, Baltimore
ROBERT C. BEARDSLEY, Woods Hole Oceanographic Institution, Woods
Hole
B. CLARK BURCHFIEL, Massachusetts Institute of Technology, Cambridge
RALPH J. CICERONE, University of California, Irvine
PETER S. EAGLESON, Massachusetts Institute of Technology, Cambridge
HELEN INGRAM, Udall Center for Public Policy Studies, Tucson
GENE E. LIKENS, New York Botanical Gardens, Millbrook
SYUKURO MANABE, Geophysics Fluid Dynamics Lab, NOAA, Princeton
JACK E. OLIVER, Cornell University, Ithaca
PHILIP A. PALMER, E.I. du Pont de Nemours & Co., Newark, Delaware
FRANK L. PARKER, Vanderbilt University, Nashville
DUNCAN T. PATTEN, Arizona State University, Tempe
MAXINE L. SAVITZ, Allied Signal Aerospace, Torrance, California
LARRY L. SMARR, University of Illinois at Urbana-Champaign, Champaign

STEVEN M. STANLEY, Case Western Reserve University, Cleveland
CRISPIN TICKELL, Green College at the Radcliffe Observatory, Oxford,
United Kingdom
KARL K. TUREKIAN, Yale University, New Haven
IRVIN L. WHITE, New York State Energy Research and Development
Authority, Albany
JAMES H. ZUMBERGE, University of Southern California, Los Angeles
Staff
STEPHEN RATTIEN, Executive Director
STEPHEN D. PARKER, Associate Executive Director
JANICE E. GREENE, Assistant Executive Director
JEANETTE A. SPOON, Financial Officer
CARLITA PERRY, Administrative Assistant

Copyright © National Academy of Sciences. All rights reserved.

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Preface

Ambient ozone in urban and regional air pollution represents one of this
country's most pervasive and stubborn environmental problems. Despite more
than two decades of massive and costly efforts to bring this problem under
control, the lack of ozone abatement progress in many areas of the country has

been disappointing and perplexing.
It is encouraging to note that the U.S. Environmental Protection Agency
recognized a need for this independent assessment from the National Research
Council and agreed to co-sponsor the study in 1989, even before it was
mandated in Section 185B of the Clean Air Act Amendments of 1990. It is
further encouraging to note the additional support for this study by the U.S.
Department of Energy, the American Petroleum Institute, and the Motor
Vehicle Manufacturers Association of the United States. The authors of this
report have undertaken an effort to re-think the problem of ambient ozone and
to suggest steps by which the nation can begin to address this problem on a
more rigorous scientific basis.
The Committee on Tropospheric Ozone Formation and Measurement was
established by the National Research Council to evaluate scientific information
relevant to precursors and tropospheric formation of ozone and to recommend
strategies and priorities for addressing the critical gaps in scientific information
necessary to help address the problem of high ozone concentrations in the lower
atmosphere. The committee was specifically charged to address emissions of
volatile organic compounds (anthropogenic and biogenic) and oxides of
nitrogen; significant photochemical reactions that form ozone, including
differences in various geographic regions; precursor emission effects

Copyright © National Academy of Sciences. All rights reserved.

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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on daily patterns of ozone concentration; ambient monitoring techniques; input
data and performance evaluations of air quality models; regional sourcereceptor relationships; statistical approaches in tracking ozone abatement
progress; and patterns of concentration, time, and interactions with other
atmospheric pollutants.
During the course of the committee's deliberations, we solicited
information from many federal, state, academic, and industrial experts. We also
reviewed the scientific literature, government agency reports, and unpublished
data bases. The committee benefitted from having earlier National Research
Council and Congressional Office of Technology Assessment reports as a
starting base. Gregory Whetstone of the House Energy and Commerce
Committee staff, John Bachmann and John Calcagni of the Environmental
Protection Agency, and representatives of the other sponsors kindly provided
useful information and perspectives to the committee. The committee's efforts
were also greatly aided by information provided by David Chock of Ford Motor
Company's Research and Engineering Division, Brian Lamb of Washington
State University, Douglas Lawson of the California Air Resources Board, S. T.
Rao of the New York State Department of Environmental Conservation, and
Donald Stedman of the University of Denver.
We wish especially to thank Raymond Wassel, the National Research
Council project director, who assisted the committee all along the way, and was
particularly valuable in the final stages of preparation of the report. We are also
grateful to James Reisa, director of the Board on Environmental Studies and
Toxicology, for his guidance and contributions throughout the study. Kate Kelly
did an excellent job as editor. Other staff who contributed greatly to the effort
were research assistant William Lipscomb, who helped in the final stages; Lee
Paulson and Tania Williams, who prepared the document for publication; Felita
Buckner, the project secretary; information specialist Anne Sprague; and other
dedicated staff of BEST's Technical Information Center.
JOHN H. SEINFELD

CHAIRMAN

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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Dedication

The committee dedicates this report to our late colleague and committee
member, Dr. Bernard J. Steigerwald, whose three decades of distinguished
public service with the United States Public Health Service the National Air
Pollution Control Administration, and the Environmental Protection Agency
contributed significantly to scientific knowledge and protection of the nation's
air quality.

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A Research Program on Tropospheric Ozone

1
1
2
3
4
4
5
6
8
9
9
11
13
14

What Is the Problem?
Natural Atmospheric Ozone
Understanding Tropospheric Ozone and Photochemical Air Pollution
Ozone and Air-Quality Regulations
National Trends in Ozone
Detrimental Effects of Ozone
Purpose of This Report

19
19
24

Copyright © National Academy of Sciences. All rights reserved.

29
30
31
38

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
/>CONTENTS

xii

2

Trends in Tropospheric Concentrations of Ozone
Introduction
National Ambient Air Quality Standard For Ozone
National Trends in Tropospheric Concentrations of Ozone
Trends in Precursor Emissions
Ozone Trends Normalized For Meteorological Variation
Summary

41
41
43
46

48
50
61

3

Criteria for Designing and Evaluating Ozone Reduction Strategies
Introduction
The Clean Air Act
The State Implementation Plan
Summary

67
67
67
74
89

4

The Effects of Meteorology on Tropospheric Ozone
Introduction
Ozone Accumulation
Clouds and Venting of Air Pollutants
Regional and Mesoscale Predictability of Ozone
Global and Long-Term Predictability of Ozone
Ozone in the Eastern United States
Summary

93

93
93
95
96
97
98
105

5

Atmospheric Chemistry of Ozone and Its Precursors
Introduction
General Schemes of Tropospheric Chemistry
Atmospheric Chemistry of Anthropogenic VOCs
Biogenic VOCs
Development and Testing of Chemical Mechanisms
Ozone Formation Potential of Various VOCs
Summary

109
109
110
130
139
149
153
160

6

VOCs and NOx: Relationship to Ozone and Associated Pollutants
Introduction
Characteristics of Ozone Isopleths
Uncertainties and Sensitivities of Isopleths

163
163
165
168

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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xiii

Other Limitations of Isopleths For Evaluation of Control Strategies
Effects of VOC and NOx Control on Other Species
Summary
7

173
175
186

Techniques for Measurement of Reactive Nitrogen Oxides, Volatile
Organic Compounds, and Oxidants
Introduction
Measurement Techniques For Oxides of Nitrogen and Their Oxidation Products
Measurement Techniques for Carbon Monoxide and Volatile
Organic Compounds
Measurement Techniques for Oxidants
Condensed-Phase Measurement Techniques
Long-Term Monitoring and Intensive Field Measurement Programs
Summary

187

8

Atmospheric Observations of VOCs, NOx, and Ozone
Introduction
Observations of Ozone
Observations of NOx
Observations of NOy
Observations of VOCs
Analysis of VOC Data Sets
Source Apportionment
Summary of VOC, NOx and Ozone Observations
Summary

211
211
212

215
221
224
231
237
247
248

9

Emissions Inventories
Introduction
Compilation of Emissions Inventories
Anthropogenic Emissions Inventories
Estimates of Biogenic Emissions
Accuracy of Emissions Inventories
Motor Vehicle Emissions
Atmospheric Measurements Versus Emissions Inventories
Summary

251
251
252
254
263
280
283
288
299

Copyright © National Academy of Sciences. All rights reserved.

187
188
194
199
203
204
208

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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10

xiv

Ozone Air-Quality Models
Introduction
Meteorological Input to Air-Quality Models
Boundary and Initial Conditions
Demonstration of Attainment
Regional Grid Models
Evaluation of Model Performance
Testing The Adequacy of Model Response to Changes in Emissions

Summary

348

11

VOC Versus NOx Controls
Introduction
EKMA-Based Studies
Grid-Based Modeling Studies
Summary

351
351
352
359
375

12

Alternative Fuels
Introduction
Fuel Choices
Attributes of Alternative Fuels
Alternative Fuels and Air Quality
Regulatory Implementation of Alternative Fuel Use
Summary

379
379

381
385
392
405
409

13

Tropospheric Ozone and Global Change
Introduction
Global Change: Observations
Global Change: Expectations and Response
Predicting Changes in Tropospheric Ozone
Summary

413
413
413
416
422
424

14

A Research Program on Tropospheric Ozone

425

References

429

Index

491

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303
303
306
310
311
315
329
346

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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xv

Tables
TABLE 1-1
TABLE 2-1

TABLE 2-3
TABLE 3-1
TABLE 3-2
TABLE 3-3
TABLE 5-1

TABLE 5-2

TABLE 5-3
TABLE 5-4

TABLE 5-5

TABLE 6-1

TABLE 6-2

TABLE 8-1
TABLE 8-2
TABLE 8-3
TABLE 8-4
TABLE 8-5
TABLE 8-6

TABLE 9-1
TABLE 9-2

Number of Areas Not Meeting the Ozone NAAQS
(1982-1989)
Attributes of an Ozone NAAQS

Parameters Affecting ''High Ozone Days''
Classification of Nonattainment Areas
Classification of Nonattainment Areas for Ozone
Maximum Technology Control Levels for VOC Area
Sources
Calculated Tropospheric Lifetimes of Selected VOCs
Due to Photolysis and Reaction with OH and NO3
Radicals and Ozone
Room-Temperature Rate Constants for the Gas-Phase
Reactions of a Series of Organic Compounds of Biogenic Origin with OH and NO 3 Radicals and Ozone
Calculated Tropospheric Lifetimes of VOCs
Calculated incremental Reactivities of CO and Selected
VOCs as a Function of the VOC/NOx Ratio for an
Eight-Component VOC Mix and Low-Dilution Conditions
Calculated Incremental Reactivities and Kinetic and
Mechanistic Reactivities for CO and Selected VOCs
for Maximum Ozone Formation Conditions, Based on
Scenarios for 12 Urban Areas in the U.S.
Speciation of VOCs for Washington, D.C., Beaumont,
Texas,
and an All-City Average Used to Generate Figures
6-2 and 6-3
Reported Mass Scattering Coefficients (ai) in Units of m2/
g for free particles containing sulfate, nitrate, and carbon in various locations
Typical Summertime Daily Maximum Ozone Concentrations
Average Concentrations Measured at Nonurban Monitoring Locations
Average Mixing Ratios Measured at Isolated Rural Sites
and Coastal Inflow Sites
Typical Boundary Layer NOx Concentrations
Speciated VOC Data Analyzed

Top 35 and Total VOCs Measured at Georgia Tech Campus, Atlanta, 1100-1400, 7/13/81 - 8/03/81 (dataset
I.A1)
Types of Point Source Emissions Data for NAPAP
Types of Area Source Emissions Data for NAPAP

Copyright © National Academy of Sciences. All rights reserved.

32
45
57
69
70
88
122

139

142
155

159

174

180

214
219
220
221

226
234

255
256

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xvi

TABLE 9-3
TABLE 9-4
TABLE 9-5
TABLE 9-6
TABLE 9-7
TABLE 9-8
TABLE 9-9
TABLE 9-10

TABLE 10-1
TABLE 10-2
TABLE 10-3
TABLE 10-4

TABLE 10-5
TABLE 11-1

TABLE 11-2

Estimated Annual U.S. NOx Emissions from Anthropogenic Sources Obtained from Recent Inventories
Compounds Identified as Emissions from the Agricultural and Natural Plant Species Studied
Emissions Factors, µg/m2-hr
Production of NOx by Lightning over the United States
as a Function of Season, Tg-N
Annual NOx Emissions from Soil by EPA Regions
Sources of Emission Variability
90% relative confidence intervals (RCI) for national
annual NOx emissions
Comparison of mobile-source contribution deduced from
emissions inventory data with estimates deduced from
ambient measurements
Photochemical Air Quality Models
Aerometric Data Base Elements
Observed Ozone Concentrations at Monitoring Sites in
Six Groupings
Average Ratio (Observation/Prediction) over Station
Groups at 50th and 90th percentiles of Cumulative
Frequency Distributions
Classes of Photochemical Models
Ozone Design Values, VOC Concentrations, VOC/NOx,
mobile source emissions, and estimated VOC control
requirements
Sensitivity of Ozone Formation to VOC Emissions

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260
264
268
275
279
281
282
293

307
313
321
329

349
354

358

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TABLE 11-3
TABLE 11-4
TABLE 11-5
TABLE 11-6
TABLE 11-7
TABLE 12-1
TABLE 12-2
TABLE 12-3

TABLE 12-4
TABLE 12-5
TABLE 12-6

TABLE 13-1
TABLE 13-2

Emissions Control Scenarios used with ROM
ROM simulations
Ozone response in Northeast to VOC and NOx Controls
found using ROM
Effect of Controls on Ozone in New York
Comparison of Nesting Techniques for Peak Ozone Predictions
Alternative Fuel Feedstocks, Cost, and Attributes
VOC Composition of Exhaust and Evaporative Emissions from Gasoline (indolene) and Alternative Fuels
Incremental Reactivities of CO and Selected VOCs in
Alternative Fuels as a Function of the VOC/NOx
Ratio for an Eight-Component VOC Mix and LowDilution Conditions, Moles Ozone/Mole Carbon
Ozone Peak and Exposure Reactivities of Compounds
Relative to Carbon Monoxide

Relative Reactivities of Emissions from Gasoline and
Alternative Fuels
California's 50,000 Mile Certification Standards for Passenger Cars and Light-Duty Trucks ≤ 3750 lb. Loaded
Vehicle Weight (g/mi)
Changing Atmospheric Composition
Links Between Human Activities, Atmospheric Changes,
and Tropospheric Ozone

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Figures
FIGURE 1-1
FIGURE 1-2
FIGURE 1-3
FIGURE 1-4

FIGURE 1-5

FIGURE 1-6

FIGURE 2-1
FIGURE 2-2

FIGURE 2-3

Typical global annual mean vertical ozone distribution
Photochemical air pollution, from emission to deposition
Conceptual canonical regions for evaluating tropospheric ozone formation and control
Trends in the mean and range of annual second highest
daily maximum 1-hour levels of ozone in Atlanta,
Los Angeles-Anaheim, and Washington, D.C.,
metropolitan areas
Three-day sequence of hourly ozone concentration at
Montague, Massachusetts. Sulfate Regional Experiment (SURE) station showing locally generated

midday peaks and transported late peaks
The diurnal variation in ozone concentration during
the summer 1982 ozone episode at Mendham, New
Jersey, associated with the health effects study conducted by Lioy et al., 1985
Areas classified as nonattainment of ozone NAAQS,
1990
Boxplot comparisons of trends in annual second highest daily maximum 1-hr ozone concentration at 431
monitoring sites, 1980-1989
National trend in the composite average of the estimated number of days exceeding the ozone
NAAQS concentration in the ozone season at monitoring sites, with 95% confidence intervals,
1979-1988

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FIGURE 2-4
FIGURE 2-5
FIGURE 2-6
FIGURE 2-7
FIGURE 2-8

FIGURE 2-9

FIGURE 2-10
FIGURE 2-11
FIGURE 2-12

FIGURE 2-13

FIGURE 3-1
FIGURE 3-2
FIGURE 3-3
FIGURE 4-1
FIGURE 4-2

FIGURE 4-3
FIGURE 4-4a

FIGURE 4-4b

FIGURE 5-1
FIGURE 5-2

FIGURE 5-3

National trend in VOC emissions, 1980-1989
National trend in NOx emissions, 1980-1989
Connecticut daily maximum ozone vs. daily maximum
temperature, 1976-1986
Ten-year trends in various ozone summary statistics
Three-year running mean of South Coast basin population-weighted ozone exposure hours for the average
resident
Three-year running mean of per capita ozone exposure
in South Coast basin (for all hours exceeding 120
ppb ozone)
Number of days exceeding the ozone NAAQS concentration in the Chicago area
Ozone and temperature trends for four cities, 1980-1988
Trends in ozone concentrations (temperature-adjusted
and unadjusted) at nine sites in the California South
Coast air basin, 1968-1985
Predicted vs. actual maximum ozone concentration for
days that passed the screening test at Bridgeport,
Connecticut
Conceptual diagram of SIP mechanism
State implementation planning process
VOC emissions reductions in 1994 and 2004 compared with 1985 emissions, by control method
Seasonal and diurnal distributions of ozone at rural

sites in the United States
24-hr cumulative probability distributions for ozone
from April 1 to Sept. 30. (a) Western NAPBN sites;
(B) eastern NAPBN sites; (c) SURE sites; (d)
Whiteface Mountain
Time series of daily maximum ozone concentrations at
rural sites in the northeastern United States in 1979
The average number of reports of ozone concentrations > 120 ppb at the combined cities of New York
and Boston from 1983 to 1985
The average number of reports of ozone concentrations > 120 ppb at the combined cities of Dallas and
Houston, from 1983 to 1985
Major reactions involved in the oxidation of methane
in the presence of NOx
Overall reaction scheme for the OH radical-initiated
degradation of isoprene [CH2=CHC(CH3)=CH4] in
the presence of NOx
Simplified diagram of the chemical processing that
occurs
among VOCs

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FIGURE 6-1
FIGURE 6-2

FIGURE 6-3

FIGURE 6-4
FIGURE 6-5
FIGURE 8-1
FIGURE 8-2a
FIGURE 8-2b
FIGURE 8-3
FIGURE 8-4

FIGURE 8-5

FIGURE 8-6

FIGURE 8-7

FIGURE 8-8

Typical ozone isopleths used in EPA's EKMA (empirical kinetic modeling approach)
Ozone (ppm) isopleths generated using the Lurman,
Carter, and Coyner (LCC) mechanism and assuming that of the total VOCs (excluding methane), the
following percentages are aldeydes: for solid lines
5% in the atmospheric boundary layer (ABL),
10.7% aloft (base case) and for broken lines 2% in
the ABL, 4.3% aloft

Ozone (PPM)isopleths generated using the Lurman,
Carter, and Coyner (LCC) mechanism and VOC
compositions (including methane) typical (Jeffries
et al., 1989) of Washington D.C. and Beaumont,
Texas
Ozone isopleths for peak ozone concentrations (ppm)
regardless of location in the Los Angeles air basin
Predicted sources of OH radicals as a function of time
of day for a typical polluted urban atmosphere
Diurnal behavior of ozone at rural sites in the United
States in July
NOx concentrations measured in urban locations in the
United States during the summer of 1984
NOx concentrations measured in urban locations in the
United States during the summer of 1984
NOy concentrations measured during the summer of
1986 at several rural sites in North America
NOy measurements made at Mauna Loa, Hawaii (Carroll et al., in press), a remote site, and Point Arena,
California (Parrish et al., 1985), Niwot Ridge, Colorado (Parrish et al., 1988; Fahey et al., 1986b), and
Scotia, Pennsylvania (Parrish et al., 1988), three
rural continental sites
Total nonmethane VOC concentrations and propylene
equivalents (Propy-Equiv) concentrations measured
at urban-suburban, rural, and remote sites from
Table 8-5
Observed atmospheric concentrations of trans-2pentene, cis-2-butene, cyclohexene, 2-methyl-2pentene, and isoprene
Observed atmospheric concentrations ratios of trans-2pentene to cis-2-butene, 2-methyl-2-pentene to
cyclohexene, isoprene to cis-2-butene, and isoprene
to cyclohexene as a function of time of day
Isoprene concentrations as function of temperature at

Pride, a suburb of Baton Rouge, and at the
Louisiana State University campus, in downtown
Baton Rouge

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xxi

FIGURE 8-9

FIGURE 8-10

FIGURE 8-11

FIGURE 8-12

FIGURE 8-13
FIGURE 9-1
FIGURE 9-2a
FIGURE 9-2b
FIGURE 9-3
FIGURE 9-4
FIGURE 9-5
FIGURE 9-6
FIGURE 9-7
FIGURE 9-8
FIGURE 9-9
FIGURE 9-10
FIGURE 9-11

FIGURE 9-12

Total nonmethane VOC in Propy-Equiv concentrations
in units of ppb carbon observed at urban-suburban
sites (midday) and rural sites (daylight hours) and
apportioned by source category
Total nonmethane VOC Propy-Equiv concentrations in
units of ppb carbon observed at the Louisiana State
University campus as a function of time of day and
apportioned by source category
Total nonmethane VOC Propy-Equiv concentrations in
units of ppb carbon observed at Glendora, a site
near Los Angeles, as a function of time of day and
apportioned by. source category
Nonmethane VOC Propy-Equiv concentrations in
units of ppb carbon apportioned by source category
using the 1985 National Acid Precipitation Assessment Program (NAPAP) speciated VOC inventory
for the nation and the California Air Resources
Board (CARB) speciated VOC inventory for the
Los Angeles area during an August day
VOC, NOx and ozone concentrations in the atmospheric boundary layer at four locations
Results of 30 NOx-emissions tests on tangentially fired
boilers that use coal
NAPAP 1985 national emissions inventory for NOx
and VOCs by source category
NAPAP 1985 national emissions inventory for NOx
and VOCs by source category
NAPAP 1985 national emissions inventory for NOx
and VOCs by state
Total nonmethane hydrocarbon emissions (NMHC) (a)
from deciduous trees and (b) from conifers

Biogenic emission sampling collection system
Nonmethane VOC emissions in Montana by season
and source type
Average nonmethane VOC flux (kg/hectare) during
the summer in the United States
VOC/NOx ratios measured in urban locations in the
United States during the summer of 1984
VOC/NOx ratios measured during summer 1985
Biogenic VOC concentrations (ppb carbon) measured
during the summers of 1984 and 1985
Percentage of biogenic VOCs compared with total
VOC measured during the summers of 1984 and
1985
Correlation between CO and NOy measured at a suburban site in Boulder

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xxii

FIGURE 9-13
FIGURE 9-14
FIGURE 9-15

FIGURE 10-1
FIGURE 10-2a
FIGURE 10-2b
FIGURE 10-3
FIGURE 10-4

FIGURE 10-5

FIGURE 10-6

FIGURE 10-7
FIGURE 10-8

FIGURE 11-1

FIGURE 11-2

FIGURE 11-3a

FIGURE 11-3b

FIGURE 11-3c

Ambient versus inventory CO/NOx ratios, South Coast
Air Basin, August 1987
Ambient versus inventory VOC/NOx, South Coast Air
Basin, August 1987
Comparison of VOC/NOx ratios derived from ambient
measurements and emissions inventories for seven
cities
Regional oxidant model (ROM) vertical structure of
the atmosphere during daytime conditions
Regional oxidant model (ROM) domain, Northeastern
United States
ROM domain, Southeastern United States

ROM grid cell locations (darkened) of monitoring sites
within groups 1 through 6 (see Table 10-3)
Observed versus ROM-predicted cumulative frequency distributions of daytime hourly ozone
concentrations at each of six groups of receptor
locations from July 14 to Aug. 31, 1980
Bias versus observed concentration for maximum
daily ozone over the simulation period from July 14
to Aug. 31, 1980, for groups 1 through 6 (see Table
10-3)
Contours of maximum hourly ozone concentrations
over the period July 25-27, 1980, for (a) observed
and (b) predicted data sets
Ozone predictions and observations; Sept. 17, 1984,
Simi monitoring station
Overall bias in hourly averaged ozone predictions by
urban area for single- and multiple-day simulations
of episodes of high concentrations of ozone for
model applications prior to 1988
Ozone isopleth diagram for three cities (A, B, and c)
that have the same peak I-hour ozone concentrations (Cp)
Ozone isopleths for locations within the Los Angeles
air basin from an airshed model for spatially uniform reductions of VOC and NOx
Maximum predicted ozone concentration (ppb) over
the six-day simulation period for the model run
with anthropogenic emissions only
Maximum predicted ozone (ppb) over the six-day simulation period, for the AB run, which contains both
anthropogenic and BEIS biogenic emissions
The six-day maximum predicted ozone concentration
(ppb) for the run with Biogenic Emissions Inventory System (BEIS) biogenic emissions and no
anthropogenic VOC emissions ("A(NOx)B")

Percentage change in episode maximum ozone concentrations, 2005 base case versus a VOC-alone reduction strategy (July 2-17, 1988)
Percentage change in episode maximum ozone concentrations, 2005 base case versus a combined NOxVOC reduction strategy (July 2-17, 1988)
Estimated nationwide VOC emissions by source category, by year
VOC emissions in nonattainment cities, by source category, 1985
NOx emissions an peak concentrations of ozone in
nonattainment cities, 1985
NOx emissions from mobile sources in 1985 as a percentage of total (mobile plus stationary) emissions
Approximate Reid vapor pressure dependence on fuel
composition
Observed trends in surface air temperatures
Vertical distribution of ozone in the troposphere immediately downwind of the east coast of the United
States

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Rethinking the Ozone Problem in Urban and Regional Air Pollution
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1

Executive Summary

INTRODUCTION
Of the six major air pollutants for which National Ambient Air Quality
Standards (NAAQS) have been designated under the Clean Air Act, the-most
pervasive problem continues to be ozone,1 the most prevalent photochemical
oxidant and an important component of "smog." The most critical aspect of this
problem is the formation of ozone in and downwind of large urban areas where,
under certain meteorological conditions, emissions of nitric oxide and nitrogen

dioxide (known together as Nor.) and volatile organic compounds (VOCs) can
result in ambient ozone concentrations up to three times the concentration
considered protective of public health by the U.S. Environmental Protection
Agency (EPA).
Major sources of VOCs in the atmosphere include motor vehicle exhaust,
emissions from the use of solvents, and emissions from the chemical and
petroleum industries. In addition, there is now a heightened appreciation of the
importance of reactive VOCs emitted by vegetation. NOx comes mainly from
the combustion of fossil fuels; major sources include motor vehicles and
electricity generating stations.
The occurrence of ozone concentrations that exceed the NAAQS in various

1 The scientific community now has strong reason to believe that, unlike stratospheric
(i.e., high-altitude) ozone concentrations, which are declining, concentrations of
tropospheric (i.e., near-ground) ozone are generally increasing over large regions of the
United States.

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