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



The National Academies | 500 Fifth St. N.W. | Washington, D.C. 20001
Copyright © National Academy of Sciences. All rights reserved.
Terms of Use and Privacy Statement



Below are the first 10 and last 10 pages of uncorrected machine-read text (when available) of this chapter, followed by the top 30 algorithmically extracted key phrases from the chapter as a whole.
Intended to provide our own search engines and external engines with highly rich, chapter-representative searchable text on the opening pages of each chapter. Because it is UNCORRECTED material, please consider the following text as a useful but insufficient proxy for the authoritative book pages.

Do not use for reproduction, copying, pasting, or reading; exclusively for search engines.

OCR for page R1
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

OCR for page R1
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. 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. Library of Congress Catalog No. 91-68142 International Standard Book Number 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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
Page vi 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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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.

OCR for page R1

OCR for page R1
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

OCR for page R1
Page xiv 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

OCR for page R1
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,  

OCR for page R1
Page xvi 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

OCR for page R1
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

OCR for page R1
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

OCR for page R1
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  

OCR for page R1
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

OCR for page R1
Page xxi 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

OCR for page R1
Page xxii 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

OCR for page R1
Page xxiii 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

OCR for page R1