National Academies Press: OpenBook
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
×

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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page ii

National Academy Press
2101 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.

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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.

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Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page iii

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 Enviornmental 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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page iv

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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page v

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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page vii

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

Page viii Cite
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page viii

on daily patterns of ozone concentration; ambient monitoring techniques; input data and performance evaluations of air quality models; regional source-receptor 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

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page ix

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.

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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There was a problem loading page R10.

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xi

Contents

Executive Summary

1

Introduction

1

The Charge to the Committee

2

The Committee's Approach to its Charge

3

Ozone in the United States

4

Ozone Trends

4

State Implementation Planning

5

Anthropogenic VOC Emissions

6

Biogenic VOC Emissions

8

Ambient Air Quality Measurements

9

Air Quality Models

9

VOC Versus NOx Control

11

Alternative Fuels For Motor Vehicles

13

A Research Program on Tropospheric Ozone

14

1 What Is the Problem?

19

Natural Atmospheric Ozone

19

Understanding Tropospheric Ozone and Photochemical Air Pollution

24

Ozone and Air-Quality Regulations

29

National Trends in Ozone

30

Detrimental Effects of Ozone

31

Purpose of This Report

38

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xii

2 Trends in Tropospheric Concentrations of Ozone

41

Introduction

41

National Ambient Air Quality Standard For Ozone

43

National Trends in Tropospheric Concentrations of Ozone

46

Trends in Precursor Emissions

48

Ozone Trends Normalized For Meteorological Variation

50

Summary

61

3 Criteria for Designing and Evaluating Ozone Reduction Strategies

67

Introduction

67

The Clean Air Act

67

The State Implementation Plan

74

Summary

89

4 The Effects of Meteorology on Tropospheric Ozone

93

Introduction

93

Ozone Accumulation

93

Clouds and Venting of Air Pollutants

95

Regional and Mesoscale Predictability of Ozone

96

Global and Long-Term Predictability of Ozone

97

Ozone in the Eastern United States

98

Summary

105

5 Atmospheric Chemistry of Ozone and Its Precursors

109

Introduction

109

General Schemes of Tropospheric Chemistry

110

Atmospheric Chemistry of Anthropogenic VOCs

130

Biogenic VOCs

139

Development and Testing of Chemical Mechanisms

149

Ozone Formation Potential of Various VOCs

153

Summary

160

6 VOCs and NOx: Relationship to Ozone and Associated Pollutants

163

Introduction

163

Characteristics of Ozone Isopleths

165

Uncertainties and Sensitivities of Isopleths

168

Page xiii Cite
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xiii

Other Limitations of Isopleths For Evaluation of Control Strategies

173

Effects of VOC and NOx Control on Other Species

175

Summary

186

7 Techniques for Measurement of Reactive Nitrogen Oxides, Volatile Organic Compounds, and Oxidants

187

Introduction

187

Measurement Techniques For Oxides of Nitrogen and Their Oxidation Products

188

Measurement Techniques for Carbon Monoxide and Volatile Organic Compounds

194

Measurement Techniques for Oxidants

199

Condensed-Phase Measurement Techniques

203

Long-Term Monitoring and Intensive Field Measurement Programs

204

Summary

208

8 Atmospheric Observations of VOCs, NOx, and Ozone

211

Introduction

211

Observations of Ozone

212

Observations of NOx

215

Observations of NOy

221

Observations of VOCs

224

Analysis of VOC Data Sets

231

Source Apportionment

237

Summary of VOC, NOx and Ozone Observations

247

Summary

248

9 Emissions Inventories

251

Introduction

251

Compilation of Emissions Inventories

252

Anthropogenic Emissions Inventories

254

Estimates of Biogenic Emissions

263

Accuracy of Emissions Inventories

280

Motor Vehicle Emissions

283

Atmospheric Measurements Versus Emissions Inventories

288

Summary

299

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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10 Ozone Air-Quality Models

303

Introduction

303

Meteorological Input to Air-Quality Models

306

Boundary and Initial Conditions

310

Demonstration of Attainment

311

Regional Grid Models

315

Evaluation of Model Performance

329

Testing The Adequacy of Model Response to Changes in Emissions

346

Summary

348

11 VOC Versus NOx Controls

351

Introduction

351

EKMA-Based Studies

352

Grid-Based Modeling Studies

359

Summary

375

12 Alternative Fuels

379

Introduction

379

Fuel Choices

381

Attributes of Alternative Fuels

385

Alternative Fuels and Air Quality

392

Regulatory Implementation of Alternative Fuel Use

405

Summary

409

13 Tropospheric Ozone and Global Change

413

Introduction

413

Global Change: Observations

413

Global Change: Expectations and Response

416

Predicting Changes in Tropospheric Ozone

422

Summary

424

14 A Research Program on Tropospheric Ozone

425

References

429

Index

491

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xv

Tables

TABLE 1-1 Number of Areas Not Meeting the Ozone NAAQS (1982-1989)

32

TABLE 2-1 Attributes of an Ozone NAAQS

45

TABLE 2-3 Parameters Affecting ''High Ozone Days''

57

TABLE 3-1 Classification of Nonattainment Areas

69

TABLE 3-2 Classification of Nonattainment Areas for Ozone

70

TABLE 3-3 Maximum Technology Control Levels for VOC Area Sources

88

TABLE 5-1 Calculated Tropospheric Lifetimes of Selected VOCs Due to Photolysis and Reaction with OH and NO3 Radicals and Ozone

122

TABLE 5-2 Room-Temperature Rate Constants for the Gas-Phase Reactions of a Series of Organic Compounds of Biogenic Origin with OH and NO3 Radicals and Ozone

139

TABLE 5-3 Calculated Tropospheric Lifetimes of VOCs

142

TABLE 5-4 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

155

TABLE 5-5 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.

159

TABLE 6-1 Speciation of VOCs for Washington, D.C., Beaumont, Texas,

 
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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and an All-City Average Used to Generate Figures 6-2 and 6-3

174

TABLE 6-2 Reported Mass Scattering Coefficients (ai) in Units of m2/g for free particles containing sulfate, nitrate, and carbon in various locations

180

TABLE 8-1 Typical Summertime Daily Maximum Ozone Concentrations

214

TABLE 8-2 Average Concentrations Measured at Nonurban Monitoring Locations

219

TABLE 8-3 Average Mixing Ratios Measured at Isolated Rural Sites and Coastal Inflow Sites

220

TABLE 8-4 Typical Boundary Layer NOx Concentrations

221

TABLE 8-5 Speciated VOC Data Analyzed

226

TABLE 8-6 Top 35 and Total VOCs Measured at Georgia Tech Campus, Atlanta, 1100-1400, 7/13/81 - 8/03/81 (dataset I.Al)

234

TABLE 9-1 Types of Point Source Emissions Data for NAPAP

255

TABLE 9-2 Types of Area Source Emissions Data for NAPAP

256

TABLE 9-3 Estimated Annual U.S. NOx Emissions from Anthropogenic Sources Obtained from Recent Inventories

260

TABLE 9-4 Compounds Identified as Emissions from the Agricultural and Natural Plant Species Studied

264

TABLE 9-5 Emissions Factors, µg/m2-hr

268

TABLE 9-6 Production of NOx by Lightning over the United States as a Function of Season, Tg-N

275

TABLE 9-7 Annual NOx Emissions from Soil by EPA Regions

279

TABLE 9-8 Sources of Emission Variability

281

TABLE 9-9 90% relative confidence intervals (RCI) for national annual NOx emissions

282

TABLE 9-10 Comparison of mobile-source contribution deduced from emissions inventory data with estimates deduced from ambient measurements

293

TABLE 10-1 Photochemical Air Quality Models

307

TABLE 10-2 Aerometric Data Base Elements

313

TABLE 10-3 Observed Ozone Concentrations at Monitoring Sites in Six Groupings

321

TABLE 10-4 Average Ratio (Observation/Prediction) over Station Groups at 50th and 90th percentiles of Cumulative Frequency Distributions

329

TABLE 10-5 Classes of Photochemical Models

349

TABLE 11-1 Ozone Design Values, VOC Concentrations, VOC/NOx, mobile source emissions, and estimated VOC control requirements

354

TABLE 11-2 Sensitivity of Ozone Formation to VOC Emissions

358

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Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xvii

TABLE 11-3 Emissions Control Scenarios used with ROM

366

TABLE 11-4 ROM simulations

367

TABLE 11-5 Ozone response in Northeast to VOC and NOx Controls found using ROM

374

TABLE 11-6 Effect of Controls on Ozone in New York

375

TABLE 11-7 Comparison of Nesting Techniques for Peak Ozone Predictions

376

TABLE 12-1 Alternative Fuel Feedstocks, Cost, and Attributes

387

TABLE 12-2 VOC Composition of Exhaust and Evaporative Emissions from Gasoline (indolene) and Alternative Fuels

396

TABLE 12-3 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 Low-Dilution Conditions, Moles Ozone/Mole Carbon

405

TABLE 12-4 Ozone Peak and Exposure Reactivities of Compounds Relative to Carbon Monoxide

406

TABLE 12-5 Relative Reactivities of Emissions from Gasoline and Alternative Fuels

407

TABLE 12-6 California's 50,000 Mile Certification Standards for Passenger Cars and Light-Duty Trucks < 3750 lb. Loaded Vehicle Weight (g/mi)

409

TABLE 13-1 Changing Atmospheric Composition

414

TABLE 13-2 Links Between Human Activities, Atmospheric Changes, and Tropospheric Ozone

418

Page xviii Cite
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xviii

Figures

FIGURE 1-1 Typical global annual mean vertical ozone distribution

20

FIGURE 1-2 Photochemical air pollution, from emission to deposition

27

FIGURE 1-3 Conceptual canonical regions for evaluating tropospheric ozone formation and control

28

FIGURE 1-4 Trends in the mean and range of annual second highest daily maximum I-hour levels of ozone in Atlanta, Los Angeles-Anaheim, and Washington, D.C., metropolitan areas

34

FIGURE 1-5 Three-day sequence of hourly ozone concentration at Montague, Massachusetts. Sulfate Regional Experiment (SURE) station showing locally generated midday peaks and transported late peaks

35

FIGURE 1-6 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

36

FIGURE 2-1 Areas classified as nonattainment of ozone NAAQS, 1990

42

FIGURE 2-2 Boxplot comparisons of trends in annual second highest daily maximum 1-hr ozone concentration at 431 monitoring sites, 1980-1989

47

FIGURE 2-3 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

48

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xix

FIGURE 2-4 National trend in VOC emissions, 1980-1989

49

FIGURE 2-5 National trend in NOx emissions, 1980-1989

50

FIGURE 2-6 Connecticut daily maximum ozone vs. daily maximum temperature, 1976-1986

51

FIGURE 2-7 Ten-year trends in various ozone summary statistics

53

FIGURE 2-8 Three-year running mean of South Coast basin population-weighted ozone exposure hours for the average resident

54

FIGURE 2-9 Three-year running mean of per capita ozone exposure in South Coast basin (for all hours exceeding 120 ppb ozone)

55

FIGURE 2-10 Number of days exceeding the ozone NAAQS concentration in the Chicago area

59

FIGURE 2-11 Ozone and temperature trends for four cities, 1980-1988

62

FIGURE 2-12 Trends in ozone concentrations (temperature-adjusted and unadjusted) at nine sites in the California South Coast air basin, 1968-1985

64

FIGURE 2-13 Predicted vs. actual maximum ozone concentration for days that passed the screening test at Bridgeport, Connecticut

65

FIGURE 3-1 Conceptual diagram of SIP mechanism

75

FIGURE 3-2 State implementation planning process

76

FIGURE 3-3 VOC emissions reductions in 1994 and 2004 compared with 1985 emissions, by control method

84

FIGURE 4-1 Seasonal and diurnal distributions ofozone at rural sites in the United States

101

FIGURE 4-2 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

102

FIGURE 4-3 Time series of daily maximum ozone concentrations at rural sites in the northeastern United States in 1979

103

FIGURE 4-4a The average number of reports of ozone concentrations > 120 ppb at the combined cities of New York and Boston from 1983 to 1985

106

FIGURE 4-4b The average number of reports of ozone concentrations > 120 ppb at the combined cities of Dallas and Houston, from 1983 to 1985

107

FIGURE 5-1 Major reactions involved in the oxidation of methane in the presence of NOx

118

FIGURE 5-2 Overall reaction scheme for the OH radical-initiated degradation of isoprene [CH2=CHC(CH3)=CH4] in the presence of NOx

148

FIGURE 5-3 Simplified diagram of the chemical processing that occurs

 
Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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Page xx

among VOCs

150

FIGURE 6-1 Typical ozone isopleths used in EPA's EKMA (empirical kinetic modeling approach)

165

FIGURE 6-2 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

171

FIGURE 6-3 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

172

FIGURE 6-4 Ozone isopleths for peak ozone concentrations (ppm) regardless of location in the Los Angeles air basin

176

FIGURE 6-5 Predicted sources of OH radicals as a function of time of day for a typical polluted urban atmosphere

179

FIGURE 8-1 Diurnal behavior of ozone at rural sites in the United States in July

213

FIGURE 8-2a NOx concentrations measured in urban locations in the United States during the summer of 1984

216

FIGURE 8-2b NOx concentrations measured in urban locations in the United States during the summer of 1984

217

FIGURE 8-3 NOy concentrations measured during the summer of 1986 at several rural sites in North America

222

FIGURE 8-4 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

223

FIGURE 8-5 Total nonmethane VOC concentrations and propylene equivalents (Propy-Equiv) concentrations measured at urban-suburban, rural, and remote sites from Table 8-5

237

FIGURE 8-6 Observed atmospheric concentrations of trans-2-pentene, cis-2-butene, cyclohexene, 2-methyl-2-pentene, and isoprene

239

FIGURE 8-7 Observed atmospheric concentrations ratios of trans-2-pentene 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

240

FIGURE 8-8 Isoprene concentrations as function of temperature at Pride, a suburb of Baton Rouge, and at the Louisiana State University campus, in downtown Baton Rouge

241

Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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FIGURE 8-9 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

243

FIGURE 8-10 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

244

FIGURE 8-11 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

245

FIGURE 8-12 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

246

FIGURE 8-13 VOC, NOx and ozone concentrations in the atmospheric boundary layer at four locations

247

FIGURE 9-1 Results of 30 NOx-emissions tests on tangentially fired boilers that use coal

253

FIGURE 9-2a NAPAP 1985 national emissions inventory for NOx and VOCs by source category

258

FIGURE 9-2b NAPAP 1985 national emissions inventory for NOx and VOCs by source category

259

FIGURE 9-3 NAPAP 1985 national emissions inventory for NOx and VOCs by state

260

FIGURE 9-4 Total nonmethane hydrocarbon emissions (NMHC) (a) from deciduous trees and (b) from conifers

266

FIGURE 9-5 Biogenic emission sampling collection system

268

FIGURE 9-6 Nonmethane VOC emissions in Montana by season and source type

270

FIGURE 9-7 Average nonmethane VOC flux (kg/hectare) during the summer in the United States

271

FIGURE 9-8 VOC/NOx ratios measured in urban locations in the United States during the summer of 1984

291

FIGURE 9-9 VOC/NOx ratios measured during summer 1985

292

FIGURE 9-10 Biogenic VOC concentrations (ppb carbon) measured during the summers of 1984 and 1985

294

FIGURE 9-11 Percentage of biogenic VOCs compared with total VOC measured during the summers of 1984 and 1985

295

FIGURE 9-12 Correlation between CO and NOy measured at a suburban site in Boulder

298

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FIGURE 9-13 Ambient versus inventory CO/NOx ratios, South Coast Air Basin, August 1987

299

FIGURE 9-14 Ambient versus inventory VOC/NOx, South Coast Air Basin, August 1987

300

FIGURE 9-15 Comparison of VOC/NOx ratios derived from ambient measurements and emissions inventories for seven cities

301

FIGURE 10-1 Regional oxidant model (ROM) vertical structure of the atmosphere during daytime conditions

317

FIGURE 10-2a Regional oxidant model (ROM) domain, Northeastern United States

318

FIGURE 10-2b ROM domain, Southeastern United States

319

FIGURE 10-3 ROM grid cell locations (darkened) of monitoring sites within groups 1 through 6 (see Table 10-3)

322

FIGURE 10-4 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

325

FIGURE 10-5 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)

330

FIGURE 10-6 Contours of maximum hourly ozone concentrations over the period July 25-27, 1980, for (a) observed and (b) predicted data sets

333

FIGURE 10-7 Ozone predictions and observations; Sept. 17, 1984, Simi monitoring station

336

FIGURE 10-8 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

337

FIGURE 11-1 Ozone isopleth diagram for three cities (A, B, and c) that have the same peak I-hour ozone concentrations (Cp)

352

FIGURE 11-2 Ozone isopleths for locations within the Los Angeles air basin from an airshed model for spatially uniform reductions of VOC and NOx

360

FIGURE 11-3a Maximum predicted ozone concentration (ppb) over the six-day simulation period for the model run with anthropogenic emissions only

362

FIGURE 11-3b Maximum predicted ozone (ppb) over the six-day simulation period, for the AB run, which contains both anthropogenic and BEIS biogenic emissions

363

FIGURE 11-3c 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")

364

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Suggested Citation:"Front Matter." National Research Council. 1991. Rethinking the Ozone Problem in Urban and Regional Air Pollution. Washington, DC: The National Academies Press. doi: 10.17226/1889.
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FIGURE 11-4a Predicted episode maximum ozone concentrations (ppb) for the 1985 base case (July 2-17, 1988)

369

FIGURE 11-4b Predicted episode maximum ozone concentrations (ppb) for the 2005 case with existing controls (July 2-17, 1988)

370

FIGURE 11-5a Percentage change in episode maximum ozone concentrations, 2005 base case versus a VOC-alone reduction strategy (July 2-17, 1988)

371

FIGURE 11-5b Percentage change in episode maximum ozone concentrations, 2005 base case versus a combined NOx-VOC reduction strategy (July 2-17, 1988)

372

FIGURE 12-1 Estimated nationwide VOC emissions by source category, by year

380

FIGURE 12-2 VOC emissions in nonattainment cities, by source category, 1985

382

FIGURE 12-3 NOx emissions an peak concentrations of ozone in nonattainment cities, 1985

383

FIGURE 12-4 NOx emissions from mobile sources in 1985 as a percentage of total (mobile plus stationary) emissions

384

FIGURE 12-5 Approximate Reid vapor pressure dependence on fuel composition

390

FIGURE 13-1 Observed trends in surface air temperatures

415

FIGURE 13-2 Vertical distribution of ozone in the troposphere immediately downwind of the east coast of the United States

420

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Rethinking the Ozone Problem in Urban and Regional Air Pollution Get This Book
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Despite more than 20 years of regulatory efforts, concern is widespread that ozone pollution in the lower atmosphere, or troposphere, threatens the health of humans, animals, and vegetation. This book discusses how scientific information can be used to develop more effective regulations to control ozone.

Rethinking the Ozone Problem in Urban and Regional Air Pollution discusses:

  • The latest data and analysis on how tropospheric ozone is formed.
  • How well our measurement techniques are functioning.
  • Deficiencies in efforts to date to control the problem.
  • Approaches to reducing ozone precursor emissions that hold the most promise.
  • What additional research is needed.

With a wealth of technical information, the book discusses atmospheric chemistry, the role of oxides of nitrogen (NOx) and volatile organic compounds (VOCs) in ozone formation, monitoring and modeling the formation and transport processes, and the potential contribution of alternative fuels to solving the tropospheric ozone problem. The committee discusses criteria for designing more effective ozone control efforts.

Because of its direct bearing on decisions to be made under the Clean Air Act, this book should be of great interest to environmental advocates, industry, and the regulatory community as well as scientists, faculty, and students.

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