Rethinking the Ozone Problem in Urban and Regional Air Pollution
NATIONAL ACADEMY PRESS
Washington, D.C. 1991
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
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
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
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
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
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
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
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.
There was a problem loading page R10.
Page xi
Contents
Executive Summary | |
Introduction | |
The Charge to the Committee | |
The Committee's Approach to its Charge | |
Ozone in the United States | |
Ozone Trends | |
State Implementation Planning | |
Anthropogenic VOC Emissions | |
Biogenic VOC Emissions | |
Ambient Air Quality Measurements | |
Air Quality Models | |
VOC Versus NOx Control | |
Alternative Fuels For Motor Vehicles | |
A Research Program on Tropospheric Ozone | |
1 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 |
Page 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 | |
3 Criteria for Designing and Evaluating Ozone Reduction Strategies | |
Introduction | |
The Clean Air Act | |
The State Implementation Plan | |
Summary | |
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 | |
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 | |
6 VOCs and NOx: Relationship to Ozone and Associated Pollutants | |
Introduction | |
Characteristics of Ozone Isopleths | |
Uncertainties and Sensitivities of Isopleths |
Page xiii
Other Limitations of Isopleths For Evaluation of Control Strategies | |
Effects of VOC and NOx Control on Other Species | |
Summary | |
7 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 | |
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 | |
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 |
Page xiv
10 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 | |
11 VOC Versus NOx Controls | |
Introduction | |
EKMA-Based Studies | |
Grid-Based Modeling Studies | |
Summary | |
12 Alternative Fuels | |
Introduction | |
Fuel Choices | |
Attributes of Alternative Fuels | |
Alternative Fuels and Air Quality | |
Regulatory Implementation of Alternative Fuel Use | |
Summary | |
13 Tropospheric Ozone and Global Change | |
Introduction | |
Global Change: Observations | |
Global Change: Expectations and Response | |
Predicting Changes in Tropospheric Ozone | |
Summary | |
14 A Research Program on Tropospheric Ozone | |
References | |
Index |
Page xv
Tables
TABLE 1-1 Number of Areas Not Meeting the Ozone NAAQS (1982-1989) | |
TABLE 2-1 Attributes of an Ozone NAAQS | |
TABLE 2-3 Parameters Affecting ''High Ozone Days'' | |
TABLE 3-1 Classification of Nonattainment Areas | |
TABLE 3-2 Classification of Nonattainment Areas for Ozone | |
TABLE 3-3 Maximum Technology Control Levels for VOC Area Sources | |
TABLE 5-1 Calculated Tropospheric Lifetimes of Selected VOCs Due to Photolysis and Reaction with OH and NO3 Radicals and Ozone | |
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 | |
TABLE 5-3 Calculated Tropospheric Lifetimes of VOCs | |
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 | |
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. | |
TABLE 6-1 Speciation of VOCs for Washington, D.C., Beaumont, Texas, |
Page xvi
and an All-City Average Used to Generate Figures 6-2 and 6-3 | |
TABLE 6-2 Reported Mass Scattering Coefficients (ai) in Units of m2/g for free particles containing sulfate, nitrate, and carbon in various locations | |
TABLE 8-1 Typical Summertime Daily Maximum Ozone Concentrations | |
TABLE 8-2 Average Concentrations Measured at Nonurban Monitoring Locations | |
TABLE 8-3 Average Mixing Ratios Measured at Isolated Rural Sites and Coastal Inflow Sites | |
TABLE 8-4 Typical Boundary Layer NOx Concentrations | |
TABLE 8-5 Speciated VOC Data Analyzed | |
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) | |
TABLE 9-1 Types of Point Source Emissions Data for NAPAP | |
TABLE 9-2 Types of Area Source Emissions Data for NAPAP | |
TABLE 9-3 Estimated Annual U.S. NOx Emissions from Anthropogenic Sources Obtained from Recent Inventories | |
TABLE 9-4 Compounds Identified as Emissions from the Agricultural and Natural Plant Species Studied | |
TABLE 9-5 Emissions Factors, µg/m2-hr | |
TABLE 9-6 Production of NOx by Lightning over the United States as a Function of Season, Tg-N | |
TABLE 9-7 Annual NOx Emissions from Soil by EPA Regions | |
TABLE 9-8 Sources of Emission Variability | |
TABLE 9-9 90% relative confidence intervals (RCI) for national annual NOx emissions | |
TABLE 9-10 Comparison of mobile-source contribution deduced from emissions inventory data with estimates deduced from ambient measurements | |
TABLE 10-1 Photochemical Air Quality Models | |
TABLE 10-2 Aerometric Data Base Elements | |
TABLE 10-3 Observed Ozone Concentrations at Monitoring Sites in Six Groupings | |
TABLE 10-4 Average Ratio (Observation/Prediction) over Station Groups at 50th and 90th percentiles of Cumulative Frequency Distributions | |
TABLE 10-5 Classes of Photochemical Models | |
TABLE 11-1 Ozone Design Values, VOC Concentrations, VOC/NOx, mobile source emissions, and estimated VOC control requirements | |
TABLE 11-2 Sensitivity of Ozone Formation to VOC Emissions |
Page xvii
TABLE 11-3 Emissions Control Scenarios used with ROM | |
TABLE 11-4 ROM simulations | |
TABLE 11-5 Ozone response in Northeast to VOC and NOx Controls found using ROM | |
TABLE 11-6 Effect of Controls on Ozone in New York | |
TABLE 11-7 Comparison of Nesting Techniques for Peak Ozone Predictions | |
TABLE 12-1 Alternative Fuel Feedstocks, Cost, and Attributes | |
TABLE 12-2 VOC Composition of Exhaust and Evaporative Emissions from Gasoline (indolene) and Alternative Fuels | |
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 | |
TABLE 12-4 Ozone Peak and Exposure Reactivities of Compounds Relative to Carbon Monoxide | |
TABLE 12-5 Relative Reactivities of Emissions from Gasoline and Alternative Fuels | |
TABLE 12-6 California's 50,000 Mile Certification Standards for Passenger Cars and Light-Duty Trucks < 3750 lb. Loaded Vehicle Weight (g/mi) | |
TABLE 13-1 Changing Atmospheric Composition | |
TABLE 13-2 Links Between Human Activities, Atmospheric Changes, and Tropospheric Ozone |
Page xviii
Figures
FIGURE 1-1 Typical global annual mean vertical ozone distribution | |
FIGURE 1-2 Photochemical air pollution, from emission to deposition | |
FIGURE 1-3 Conceptual canonical regions for evaluating tropospheric ozone formation and control | |
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 | |
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 | |
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 | |
FIGURE 2-1 Areas classified as nonattainment of ozone NAAQS, 1990 | |
FIGURE 2-2 Boxplot comparisons of trends in annual second highest daily maximum 1-hr ozone concentration at 431 monitoring sites, 1980-1989 | |
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 |
Page xix
FIGURE 2-4 National trend in VOC emissions, 1980-1989 | |
FIGURE 2-5 National trend in NOx emissions, 1980-1989 | |
FIGURE 2-6 Connecticut daily maximum ozone vs. daily maximum temperature, 1976-1986 | |
FIGURE 2-7 Ten-year trends in various ozone summary statistics | |
FIGURE 2-8 Three-year running mean of South Coast basin population-weighted ozone exposure hours for the average resident | |
FIGURE 2-9 Three-year running mean of per capita ozone exposure in South Coast basin (for all hours exceeding 120 ppb ozone) | |
FIGURE 2-10 Number of days exceeding the ozone NAAQS concentration in the Chicago area | |
FIGURE 2-11 Ozone and temperature trends for four cities, 1980-1988 | |
FIGURE 2-12 Trends in ozone concentrations (temperature-adjusted and unadjusted) at nine sites in the California South Coast air basin, 1968-1985 | |
FIGURE 2-13 Predicted vs. actual maximum ozone concentration for days that passed the screening test at Bridgeport, Connecticut | |
FIGURE 3-1 Conceptual diagram of SIP mechanism | |
FIGURE 3-2 State implementation planning process | |
FIGURE 3-3 VOC emissions reductions in 1994 and 2004 compared with 1985 emissions, by control method | |
FIGURE 4-1 Seasonal and diurnal distributions ofozone at rural sites in the United States | |
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 | |
FIGURE 4-3 Time series of daily maximum ozone concentrations at rural sites in the northeastern United States in 1979 | |
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 | |
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 | |
FIGURE 5-1 Major reactions involved in the oxidation of methane in the presence of NOx | |
FIGURE 5-2 Overall reaction scheme for the OH radical-initiated degradation of isoprene [CH2=CHC(CH3)=CH4] in the presence of NOx | |
FIGURE 5-3 Simplified diagram of the chemical processing that occurs |
Page xx
among VOCs | |
FIGURE 6-1 Typical ozone isopleths used in EPA's EKMA (empirical kinetic modeling approach) | |
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 | |
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 | |
FIGURE 6-4 Ozone isopleths for peak ozone concentrations (ppm) regardless of location in the Los Angeles air basin | |
FIGURE 6-5 Predicted sources of OH radicals as a function of time of day for a typical polluted urban atmosphere | |
FIGURE 8-1 Diurnal behavior of ozone at rural sites in the United States in July | |
FIGURE 8-2a NOx concentrations measured in urban locations in the United States during the summer of 1984 | |
FIGURE 8-2b NOx concentrations measured in urban locations in the United States during the summer of 1984 | |
FIGURE 8-3 NOy concentrations measured during the summer of 1986 at several rural sites in North America | |
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 | |
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 | |
FIGURE 8-6 Observed atmospheric concentrations of trans-2-pentene, cis-2-butene, cyclohexene, 2-methyl-2-pentene, and isoprene | |
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 | |
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 |
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 | |
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 | |
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 | |
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 | |
FIGURE 8-13 VOC, NOx and ozone concentrations in the atmospheric boundary layer at four locations | |
FIGURE 9-1 Results of 30 NOx-emissions tests on tangentially fired boilers that use coal | |
FIGURE 9-2a NAPAP 1985 national emissions inventory for NOx and VOCs by source category | |
FIGURE 9-2b NAPAP 1985 national emissions inventory for NOx and VOCs by source category | |
FIGURE 9-3 NAPAP 1985 national emissions inventory for NOx and VOCs by state | |
FIGURE 9-4 Total nonmethane hydrocarbon emissions (NMHC) (a) from deciduous trees and (b) from conifers | |
FIGURE 9-5 Biogenic emission sampling collection system | |
FIGURE 9-6 Nonmethane VOC emissions in Montana by season and source type | |
FIGURE 9-7 Average nonmethane VOC flux (kg/hectare) during the summer in the United States | |
FIGURE 9-8 VOC/NOx ratios measured in urban locations in the United States during the summer of 1984 | |
FIGURE 9-9 VOC/NOx ratios measured during summer 1985 | |
FIGURE 9-10 Biogenic VOC concentrations (ppb carbon) measured during the summers of 1984 and 1985 | |
FIGURE 9-11 Percentage of biogenic VOCs compared with total VOC measured during the summers of 1984 and 1985 | |
FIGURE 9-12 Correlation between CO and NOy measured at a suburban site in Boulder |
Page xxii
FIGURE 9-13 Ambient versus inventory CO/NOx ratios, South Coast Air Basin, August 1987 | |
FIGURE 9-14 Ambient versus inventory VOC/NOx, South Coast Air Basin, August 1987 | |
FIGURE 9-15 Comparison of VOC/NOx ratios derived from ambient measurements and emissions inventories for seven cities | |
FIGURE 10-1 Regional oxidant model (ROM) vertical structure of the atmosphere during daytime conditions | |
FIGURE 10-2a Regional oxidant model (ROM) domain, Northeastern United States | |
FIGURE 10-2b ROM domain, Southeastern United States | |
FIGURE 10-3 ROM grid cell locations (darkened) of monitoring sites within groups 1 through 6 (see Table 10-3) | |
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 | |
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) | |
FIGURE 10-6 Contours of maximum hourly ozone concentrations over the period July 25-27, 1980, for (a) observed and (b) predicted data sets | |
FIGURE 10-7 Ozone predictions and observations; Sept. 17, 1984, Simi monitoring station | |
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 | |
FIGURE 11-1 Ozone isopleth diagram for three cities (A, B, and c) that have the same peak I-hour ozone concentrations (Cp) | |
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 | |
FIGURE 11-3a Maximum predicted ozone concentration (ppb) over the six-day simulation period for the model run with anthropogenic emissions only | |
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 | |
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") |
Page xxiii
FIGURE 11-4a Predicted episode maximum ozone concentrations (ppb) for the 1985 base case (July 2-17, 1988) | |
FIGURE 11-4b Predicted episode maximum ozone concentrations (ppb) for the 2005 case with existing controls (July 2-17, 1988) | |
FIGURE 11-5a Percentage change in episode maximum ozone concentrations, 2005 base case versus a VOC-alone reduction strategy (July 2-17, 1988) | |
FIGURE 11-5b Percentage change in episode maximum ozone concentrations, 2005 base case versus a combined NOx-VOC reduction strategy (July 2-17, 1988) | |
FIGURE 12-1 Estimated nationwide VOC emissions by source category, by year | |
FIGURE 12-2 VOC emissions in nonattainment cities, by source category, 1985 | |
FIGURE 12-3 NOx emissions an peak concentrations of ozone in nonattainment cities, 1985 | |
FIGURE 12-4 NOx emissions from mobile sources in 1985 as a percentage of total (mobile plus stationary) emissions | |
FIGURE 12-5 Approximate Reid vapor pressure dependence on fuel composition | |
FIGURE 13-1 Observed trends in surface air temperatures | |
FIGURE 13-2 Vertical distribution of ozone in the troposphere immediately downwind of the east coast of the United States |