Fundamentals of Air Pollution FOURTH EDITION

Transcription

1 Fundamentals of Air Pollution FOURTH EDITION

2 Authors of Third Edition RICHARD W. BOUBEL Department of Mechanical Engineering Oregon State University Corvallis, Oregon DONALD L. FOX Department of Environmental Science School of Public Health University of North Carolina Chapel Hill, North Carolina D. BRUCE TURNER Trinity Consultants, Inc. Chapel Hill, North Carolina ARTHUR C. STERN (14 March April 1992)

3 Fundamentals of Air Pollution FOURTH EDITION DANIEL A. VALLERO Civil and Environmental Engineering Department Pratt School of Engineering Duke University Durham, North Carolina AMSTERDAM BOSTON HEIDELBERG LONDON NEW YORK OXFORD PARIS SAN DIEGO SAN FRANCISCO SINGAPORE SYDNEY TOKYO Academic Press is an imprint of Elsevier

4 Academic Press is an imprint of Elsevier 30 Corporate Drive, Suite 400, Burlington, MA 01803, USA 525 B Street, Suite 1900, San Diego, California , USA 84 Theobald s Road, London WC1X 8RR, UK This book is printed on acid-free paper. First Edition 1973 Second Edition 1984 Third Edition 1994 Fourth Edition 2008 Copyright 2008, Elsevier Inc. All rights reserved. No part of this publication may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopy, recording, or any information storage and retrieval system, without permission in writing from the publisher. Permissions may be sought directly from Elsevier s Science & Technology Rights Department in Oxford, UK: phone: ( 44) , fax: ( 44) ; permissions@elsevier.com. You may also complete your request online via the Elsevier homepage ( by selecting Support & Contact then Copyright and Permission and then Obtaining Permissions. Library of Congress Cataloging-in-Publication Data Vallero, Daniel A. Fundamentals of air pollution / Daniel A. Vallero 4th ed. p. cm. Includes index. ISBN (alk. paper) 1. Air Pollution. I. Title. TD883.V dc British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library ISBN: For information on all Academic Press publications visit our website at Typeset by Charon Tec Ltd (A Macmillan Company), Chennai, India Printed and bound in the USA

5 Dedicated to the four authors of the previous edition. I am standing on the shoulders of giants.

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7 Contents Preface to the Third Edition Preface to the Fourth Edition xvii xxi Part I Air Pollution Essentials 1 The Changing Face of Air Pollution I. Defining Air Pollution 3 II. The Emergence of Air Pollution Science, Engineering, and Technology 7 III. Air Pollution Before the Industrial Revolution 37 IV. Air Pollution and the Industrial Revolution 40 V. Recent Air Pollution 42 VI. The 1980s 47 VII. Recent History 48 VIII. The Future 49 Further Reading 49 Suggested Reading 51 Questions 51 vii

8 viii Contents 2 The Earth s Atmosphere I. The Atmosphere 52 II. Baseline Conditions: Unpolluted Air 53 III. What is Air Pollution? 58 IV. Particulate Matter 59 V. Concepts 71 References 76 Suggested Reading 76 Questions 76 3 Scales of the Air Pollution Problem I. Local 77 II. Urban 78 III. Regional 79 IV. Continental 80 V. Global 85 Suggested Reading 86 Questions 87 Part II The Physics and Chemistry of Air Pollution 4 Air Pollution Physics I. Mechanics of Air Pollution 93 II. Fluid Properties 95 Questions The Physics of the Atmosphere I. Energy 123 II. Motion 131 III. Energy-Motion Relationships 137 IV. Local Wind Systems 141 V. General Circulation 148 References 152 Suggested Reading 152 Questions Air Pollution Systems and Processes I. Chemical Processes in Air Pollution 154

9 Contents ix II. Air Pollution Chemodynamics 160 References 197 Suggested Reading 197 Questions Characterizing Air Pollution I. Relationship Between Physics and Chemistry 199 II. Basic Chemical Concepts 200 III. Expressions of Chemical Characteristics 207 IV. Electromagnetic Radiation, Electron Density, Orbitals, and Valence 210 V. Organic Chemistry 238 VI. Introduction to Atmospheric Chemistry 248 VII. Heterogeneous Reactions 259 VIII. Scavenging and Removal from the Atmosphere 259 References 260 Suggested Reading 261 Questions Air Quality I. Averaging Time 267 II. Cycles 270 III. Primary and Secondary Pollutants 273 IV. Measurement Systems 275 V. Air Quality Levels 277 References 295 Suggested Reading 295 Questions The Philosophy of Air Pollution Control I. Strategy and Tactics: The Air Pollution System 296 II. Episode Control 301 III. Air Quality Management Control Strategy 306 IV. Alternative Control Strategies 309 V. Economic Considerations 310 References 311 Suggested Reading 311 Questions Sources of Air Pollution I. General 313 II. Combustion 319 III. Stationary Sources 325

10 x Contents IV. Mobile Sources 336 V. Air Toxics Sources 337 VI. Emission Inventory 343 VII. An International Perspective: Differences in Time and Space 346 VIII. ODORS: More than just a Nuisance 351 References 353 Suggested Reading 353 Questions 354 Part III Risks from Air Pollution 11 Effects on Health and Human Welfare I. Air Water Soil Interactions 359 II. Total Body Burden 365 III. The Human Respiratory System 378 IV. Impact of Air Pollution on Humans 381 V. Impact of Odor on Humans 394 References 395 Suggested Reading 395 Questions Effects on Vegetation and Animals I. Injury versus Damage 397 II. Effects on Vegetation and Crops 399 III. Effects on Forests 403 IV. Effects on Animals 408 References 411 Suggested Reading 412 Questions Effects on Materials and Structures I. Effects on Metals 413 II. Effects on Stone 416 III. Effects on Fabrics and Dyes 417 IV. Effects on Leather, Paper, Paint, and Glass 419 V. Effects on Rubber 420 References 421 Suggested Reading 422 Questions 422

11 Contents xi 14 Effects on the Atmosphere, Soil, and Water Bodies I. The Physics of Visibility 423 II. Formation of Atmospheric Haze 430 III. Effects of Atmospheric Haze 433 IV. Visibility 434 V. Acidic Deposition 435 VI. Effects of Acidic Deposition 438 References 439 Suggested Reading 440 Questions Long-Term Effects on the Planet I. Global Climate Change 442 II. Ozone Holes 451 References 453 Suggested Reading 454 Questions 454 Part IV The Measurement and Monitoring of Air Pollution 16 Ambient Air Sampling I. Elements of a Sampling System 457 II. Sampling Systems for Gaseous Pollutants 459 III. Sampling Systems for Particulate Pollutants 463 IV. Passive Sampling Systems 466 V. Sampler Siting Requirements 468 VI. Sampling for Air Toxics 469 References 470 Suggested Reading 470 Questions Ambient Air Pollutants: Analysis and Measurement I. Analysis and Measurement of Gaseous Pollutants 472 II. Analysis and Measurement of Particulate Pollutants 487 III. Analysis and Measurement of Odors 490 IV. Analysis and Measurement of Visibility 492 V. Analysis and Measurement of Acidic Deposition 496 References 497 Suggested Reading 498 Questions 498

12 xii Contents 18 Air Pollution Monitoring and Surveillance I. Stationary Monitoring Networks 500 II. Mobile Monitoring and Surveillance 503 III. Remote Sensing 505 IV. Personal Monitoring 506 V. Quality Assurance 508 VI. Data Analysis and Display 510 References 513 Suggested Reading 513 Questions Air Pathways from Hazardous Waste Sites I. Introduction 515 II. Multimedia Transport 516 III. Contaminant Fate Analysis 516 IV. Modeling 524 V. Assessment of a Hazardous Waste Site 525 References 533 Suggested Reading 533 Questions 533 Part V Air Pollution Modeling 20 The Meteorological Bases of Atmospheric Pollution I. Ventilation 537 II. Stagnation 539 III. Meteorological Conditions during Historic Pollution Episodes 540 IV. Effects of Pollution on the Atmosphere 546 V. Removal Mechanisms 547 References 550 Suggested Reading 551 Questions Transport and Dispersion of Air Pollutants I. Wind Velocity 552 II. Turbulence 554 III. Estimating Concentrations from Point Sources 557 IV. Dispersion Instrumentation 566

13 Contents xiii V. Atmospheric Tracers 571 VI. Concentration Variation with Averaging Time 576 References 578 Suggested Reading 579 Questions Air Pollution Modeling and Prediction I. Plume Rise 582 II. Modeling Techniques 585 III. Modeling Nonreactive Pollutants 587 IV. Modeling Pollutant Transformations 590 V. Modeling Air Pollutants 593 VI. Model Performance, Accuracy, and Utilization 627 References 633 Suggested Reading 636 Questions Air Pollution Climatology I. Sources of Data 638 II. Representativeness 641 III. Frequency of Atmospheric Stagnations 646 IV. Ventilation Climatology 647 V. Wind and Pollution Roses 650 References 654 Suggested Reading 655 Questions 655 Part VI The Regulatory Control of Air Pollution 24 Air Quality Criteria and Standards I. Air Quality Criteria 659 II. Conversion of Effects Data and Criteria to Standards 659 III. Conversion of Physical Data and Criteria to Standards 669 IV. Conversion of Biological Data and Criteria to Standards 671 V. Air Quality Standards 672 Suggested Reading 677 Questions Indoor Air Quality I. Changing Times 679 II. Factors Influencing Indoor Air Quality 680

14 xiv Contents III. Indoor Air Pollutants 682 IV. Effects of Indoor Air Pollutants 685 V. Control of Indoor Air Pollutants 687 References 692 Suggested Reading 692 Questions Regulating Air Pollution I. Introduction 696 II. Titles 697 References 706 Suggested Reading 706 Questions Emission Standards I. Subjective Standards 707 II. Objective Standards 709 III. Types of Emission Standards 713 IV. Variant Forms of Emission Standards 713 V. Means for Implementing Emission Standards 715 References 721 Suggested Reading 721 Questions The Elements of Regulatory Control I. Control of New Stationary Sources 724 II. Control of Existing Stationary Sources 725 III. Control of Mobile Sources 726 IV. Air Quality Control Regions 727 V. Tall Stacks and Intermittent and Supplementary Control Systems 728 References 729 Suggested Reading 729 Questions Organization for Air Pollution Control I. Functions 730 II. Organization 733 III. Finance 736 IV. Advisory Groups 737 Suggested Readings 738 Questions 739

15 Contents xv Part VII Preventing and Controlling Air Pollution 30 Preventing Air Pollution I. Introduction 743 II. Sustainability 743 III. Green Engineering and Sustainability 744 IV. Life Cycle Analysis 753 V. Pollution Prevention 756 VI. Motivations for Practicing Green Engineering 761 VII. Future People 767 References 770 Suggested Reading 772 Questions Engineering Control Concepts I. Introduction 774 II. Process Change 776 III. Fuel Change 777 IV. Pollution Removal 778 V. Disposal of Pollutants 780 References 784 Suggested Reading 784 Questions Control Devices, Technologies, and Systems I. Introduction 786 II. Removal of Dry PM 794 III. Removal of Liquid Droplets and Mists 807 IV. Removal of Gaseous Pollutants 810 V. Removal of Odors 821 References 822 Suggested Reading 823 Questions Control of Hazardous Air Pollutants I. Air Quality and Hazardous Wastes 825 II. Pre-control Considerations 830 III. Contaminant Treatment and Control Approaches 832 IV. Thermal Treatment Processes 835 V. Thermal Destruction Systems 839

16 xvi Contents VI. Destruction Removal 844 VII. Other Thermal Processes 845 VIII. Indirect Air Impacts 848 References 849 Suggested Reading 850 Questions Control of Stationary Sources I. Introduction 852 II. Energy, Power, and Incineration 853 III. Chemical and Metallurgical Industries 859 IV. Agriculture and Forest Products Industries 872 V. Other Industrial Processes 878 References 883 Suggested Reading 884 Questions Control of Mobile Sources I. Introduction 886 II. Gasoline-Powered Vehicles 886 III. Diesel-Powered Vehicles 889 IV. Gas Turbines and Jet Engines 889 V. Alternatives to Existing Mobile Sources 891 References 893 Suggested Reading 893 Questions Source Sampling and Monitoring I. Introduction 895 II. Source Sampling 895 III. Statistics of Sampling 897 IV. The Source Test 899 V. Source Monitoring 910 References 915 Suggested Reading 915 Questions The Future of Air Pollution I. The Good News 917 II. Stubborn Problems and Innovative Solutions 917 Index 919

17 Preface to the Third Edition The authors of this book include a chemist (Donald L. Fox), a meteorologist (D. Bruce Turner), and a mechanical engineer (Richard W. Boubel). This 1:1:1 ratio has some relevance in that it approximates the ratio of those professionally involved in the field of air pollution. In the environmental protection and management field, the experience of the recent past has been that physicists and electrical engineers have been most attracted to the radiation, nuclear, and noise areas; biologists and civil engineers to the aquatic and solid waste areas; chemists, meteorologists, and chemical and mechanical engineers to the area of air pollution and its control. These remarks are not intended to exclude all others from the party (or from this course). The control of air pollution requires the combined efforts of all the professions mentioned, in addition to the input of physicians, lawyers, and social scientists. However, the professional mix of the authors, and their expectation of a not-too-dissimilar mix of students using this book, forewarns the tenor of its contents and presentation. Although this book consists of six parts and three authors, it is not to be considered six short books put together back-to-back to make one large one. By and large, the several parts are the work of more than one author. Obviously, the meteorologist member of the author team is principally responsible for the part of the book concerned with the meteorology of air pollution, the chemist author for the chapters on chemistry, and the engineer author for those on engineering. However, as you will see, no chapters are signed, and all authors xvii

18 xviii Preface to the Third Edition accept responsibility for the strengths and weaknesses of the chapters and for the book as a whole. In the 20 years since publication of the first edition of Fundamentals of Air Pollution (1973), and the 9 years since the second edition (1984), the fundamentals have not changed. The basic physics, chemistry, and engineering are still the same, but there is now a greater in-depth understanding of their application to air pollution. This edition has been edited, revised, and updated to include the new technology available to air pollution practitioners. Its contents are also influenced to a great extent by the passage of the US Clean Air Act Amendments of 1990 (CAAA90). These amendments have changed the health and risk-based regulations of the US Clean Air Act to technology-driven regulations with extensive penalty provisions for noncompliance. We have added more detailed discussion of areas that have been under intensive study during the past decade. There has been a similar need to add discussion of CAAA90 and its regulatory concepts, such as control of air toxics, indoor air pollution, pollution prevention, and trading and banking of emission rights. Ten more years of new data on air quality have required the updating of the tables and figures presenting these data. We have expanded some subject areas, which previously were of concern to only a few scientists, but which have been popularized by the media to the point where they are common discussion subjects. These include Global Warming, The Ozone Hole, Energy Conservation, Renewable Resources, and Quality of Life. With each passing decade, more and more pollution sources of earlier decades become obsolete and are replaced by processes and equipment that produce less pollution. At the same time, population and the demand for products and services increase. Students must keep these concepts in mind as they study from this text, knowing that the world in which they will practice their profession will be different from the world today. The viewpoint of this book is first that most of the students who elect to receive some training in air pollution will have previously taken courses in chemistry at the high school or university level, and that those few who have not would be well advised to defer the study of air pollution until they catch up on their chemistry. The second point of view is that the engineering design of control systems for stationary and mobile sources requires a command of the principles of chemical and mechanical engineering beyond that which can be included in a one-volume textbook on air pollution. Before venturing into the field of engineering control of air pollution, a student should, as a minimum, master courses in internal combustion engines, power plant engineering, the unit processes of chemical engineering, engineering thermodynamics, and kinetics. However, this does not have to be accomplished before taking a course based on this book but can well be done simultaneously with or after doing so. The third point of view is that no one, regardless of their professional background, should be in the field of air pollution control unless they sufficiently

19 Preface to the Third Edition xix understand the behavior of the atmosphere, which is the feature that differentiates air pollution from the other aspects of environmental protection and management. This requires a knowledge of some basic atmospheric chemistry in addition to some rather specialized air pollution meteorology. The viewpoint presented in the textbook is that very few students using it will have previously studied basic meteorology. It is hoped that exposure to air pollution meteorology at this stage will excite a handful of students to delve deeper into the subject. Therefore, a relatively large proportion of this book has been devoted to meteorology because of its projected importance to the student. The authors have tried to maintain a universal point of view so that the material presented would be equally applicable in all the countries of the world. Although a deliberate attempt has been made to keep American provincialism out of the book, it has inevitably crept in through the exclusive use of English language references and suggested reading lists, and the preponderant use of American data for the examples, tables, and figures. The saving grace in this respect is that the principles of chemistry, meteorology, and engineering are universal. As persons who have dedicated all or significant parts of their professional careers to the field of air pollution, the authors believe in its importance and relevance. We believe that as the world s population increases, it will become increasingly important to have an adequate number of welltrained professions engaged in air pollution control. If we did not believe this, it would have been pointless for us to have written this textbook. We recognize that, in terms of short-term urgency, many nations and communities may rightly assign a lower priority to air pollution control than to problems of population, poverty, nutrition, housing, education, water supply, communicable disease control, civil rights, mental health, aging, or crime. Air pollution control is more likely to have a higher priority for a person or a community already reaping the benefits of society in the form of adequate income, food, housing, education, and health care than for persons who have not and may never reap these benefits. However, in terms of long-term needs, nations and communities can ignore air pollution control only at their peril. A population can subsist, albeit poorly, with inadequate housing, schools, police, and care of the ill, insane, and aged; it can also subsist with a primitive water supply. The ultimate determinants for survival are its food and air supplies. Conversely, even were society to succeed in providing in a completely adequate manner all of its other needs, it would be of no avail if the result were an atmosphere so befouled as not to sustain life. The long-term objective of air pollution control is to allow the world s population to meet all its needs for energy, goods, and services without sullying its air supply.

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21 Preface to the Fourth Edition In the Preface to the Third Edition of this book, Donald L. Fox, D. Bruce Turner, and Richard W. Boubel expressed the importance of a multidisciplinary approach to air pollution. I wholeheartedly agree. Nothing has changed in this regard, making it a daunting challenge to update the impressive work of these renowned experts (as well as the late Arthur C. Stern in previous editions). It was easier to add new material than to remove old material. A new edition is an optimization exercise. The book must not change so much that professors using it have to change the course structure so severely that it constitutes a completely new text. On the other hand, a text must be up to date in terms of current technologies and programs, as well as in addressing threats on the horizon. Over a decade has passed since the publication of previous version. From a regulatory perspective, this is a very long time. By conventional measures, such as the National Ambient Air Quality Standards, the past decade has been very successful. But, science marches on. I recall that in the 1970s, detection in the parts per million (ppm) was impossible for most compounds. During the 1980s detection limits continued to decrease. Now, detections have improved to allow for measurements below parts per billion for many compounds. We have also witnessed sea changes in risk assessment and management. For example, the US Environmental Protection Agency laboratories were realigned to address risks, with separate laboratories to conduct research exposure, effects, risk characterization, and risk reduction. xxi

22 xxii Preface to the Fourth Edition Indeed, the previous authors were quite prescient in predicting the effects of the then newly amended Clean Air Act. The major changes started to kick in as the focus moved from technology-based approaches (best available and maximum achievable control technologies) to risk-based decision-making (residual risks remaining even after the required control technologies). The fundamentals of the science underlying air pollution have not changed, but their applications and the appreciation of their impacts have. For example, I have endeavored to enhance the discussion and explanation of the physical and chemical processes at work, particularly those related to air toxics. This has been a tendency through all four editions. New technologies must be explained, better models and computational methods have become available, analytical procedures have evolved and improved, and acute and chronic effects have become better understood. All of these have enhanced the science and engineering knowledge available to practitioners, teachers, and students. And, the savvy of the lay public about air pollution has grown substantially during the previous decade. I am indebted to my fellow scientists and engineers for their insights and comments on how to incorporate the new trends. I particularly want to note Alan Huber, who shared his work in atmospheric dispersion modeling, especially computational fluid dynamics. Others include Russ Bullock (mercury fate and transport), Paul Lioy and Panos Georgopoulos (modeling), Mark Wiesner (nanotechnology), John Kominsky and Mike Beard (asbestos), and Aarne Vesilind (history). As in previous editions, my expectation is that the reader has received some formal background in chemistry. I agree with the previous authors that anyone interested in air pollution must have a solid grounding in chemistry and the physical sciences. Without it, there is no way of knowing whether a rule or policy is plausible. I have seen too many instances of junk science in environmental decision-making. Often, these are underlain with good intentions. But, so-called advocacy does not obviate the need for sound science. That said, with a bit of effort, much of this edition can be a useful tool to any audience who is motivated to understand the what, how and why of air pollution. Another trend that I have hoped to capture is the comprehensiveness needed to address air quality. A problem need not occur if the processes leading to air pollution are approached from a life cycle or green perspective. This goes beyond pollution prevention and calls for an integrated and sustainable view. I have dedicated an entire chapter to this emergent environmental expectation. The authors of the previous edition introduced discussions about some emerging continental and global threats to the atmosphere. Since then, the urgency of some has abated (e.g. acid rain and some threats to the ozone layer), some have increased in concern (e.g. global warming), and others have continued but the contaminants of concern have varied (long-range transport of persistent chemicals). The scientific credibility of arguments

23 Preface to the Fourth Edition xxiii for and against regulatory and other actions has been uneven. The best defense against bad policy decisions is a strong foundation in the physical sciences. Let me rephrase that a bit more proactively and optimistically: My overall objective of this book is to give you, the reader, the ability to design and apply the tools needed to improve and sustain the quality of the air we breathe for many decades. These tools can only be trusted if they are thoroughly grounded in the Fundamentals of Air Pollution. DAV