Fundamentals of Air Pollution - Elsevier · 2013-12-20 · Fundamentals of Air Pollution FOURTH...

Fundamentals of

Air PollutionFOURTH EDITION

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Authors of Third Edition

RICHARD W. BOUBELDepartment of Mechanical Engineering

Oregon State UniversityCorvallis, Oregon

DONALD L. FOXDepartment of Environmental Science

School of Public HealthUniversity of North CarolinaChapel Hill, North Carolina

D. BRUCE TURNERTrinity Consultants, Inc.

Chapel Hill, North Carolina

ARTHUR C. STERN(14 March 1909–17 April 1992)

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Fundamentalsof

Air PollutionFOURTH EDITION

DANIEL A. VALLERO

Civil and Environmental Engineering DepartmentPratt School of Engineering

Duke UniversityDurham, North Carolina

AMSTERDAM • BOSTON • HEIDELBERG • LONDON • NEW YORK • OXFORD

PARIS • SAN DIEGO • SAN FRANCISCO • SINGAPORE • SYDNEY • TOKYO

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Library of Congress Cataloging-in-Publication DataVallero, Daniel A.

Fundamentals of air pollution / Daniel A. Vallero — 4th ed.p. cm.

Includes index.ISBN 978-0-12-373615-4 (alk. paper)1. Air—Pollution. I. Title.

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�

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Dedicated to the four authors of the previous edition.

I am standing on the shoulders of giants.

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Contents

Preface to the Third Edition xviiPreface to the Fourth Edition xxi

Part I

Air Pollution Essentials

1 The Changing Face of Air Pollution

I. Defining Air Pollution 3II. The Emergence of Air Pollution Science, Engineering, and

Technology 7III. Air Pollution Before the Industrial Revolution 37IV. Air Pollution and the Industrial Revolution 40V. Recent Air Pollution 42

VI. The 1980s 47VII. Recent History 48

VIII. The Future 49Further Reading 49Suggested Reading 51Questions 51

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2 The Earth’s Atmosphere

I. The Atmosphere 52II. Baseline Conditions: Unpolluted Air 53III. What is Air Pollution? 58IV. Particulate Matter 59V. Concepts 71

References 76Suggested Reading 76Questions 76

3 Scales of the Air Pollution Problem

I. Local 77II. Urban 78III. Regional 79IV. Continental 80V. Global 85

Suggested Reading 86Questions 87

Part II

The Physics and Chemistry of Air Pollution

4 Air Pollution Physics

I. Mechanics of Air Pollution 93II. Fluid Properties 95Questions 122

5 The Physics of the Atmosphere

I. Energy 123II. Motion 131III. Energy-Motion Relationships 137IV. Local Wind Systems 141V. General Circulation 148


6 Air Pollution Systems and Processes

I. Chemical Processes in Air Pollution 154

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II. Air Pollution Chemodynamics 160References 197Suggested Reading 197Questions 198

7 Characterizing Air Pollution

I. Relationship Between Physics and Chemistry 199II. Basic Chemical Concepts 200

III. Expressions of Chemical Characteristics 207IV. Electromagnetic Radiation, Electron Density, Orbitals,

and Valence 210V. Organic Chemistry 238

VI. Introduction to Atmospheric Chemistry 248VII. Heterogeneous Reactions 259VIII. Scavenging and Removal from the Atmosphere 259References 260Suggested Reading 261Questions 261

8 Air Quality

I. Averaging Time 267II. Cycles 270III. Primary and Secondary Pollutants 273IV. Measurement Systems 275V. Air Quality Levels 277


9 The Philosophy of Air Pollution Control

I. Strategy and Tactics: The Air Pollution System 296II. Episode Control 301III. Air Quality Management Control Strategy 306IV. Alternative Control Strategies 309V. Economic Considerations 310


10 Sources of Air Pollution

I. General 313II. Combustion 319III. Stationary Sources 325

Contents ix

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IV. Mobile Sources 336V. Air Toxics Sources 337

VI. Emission Inventory 343VII. An International Perspective: Differences in

Time and Space 346VIII. ODORS: More than just a Nuisance 351References 353Suggested Reading 353Questions 354

Part III

Risks from Air Pollution

11 Effects on Health and Human Welfare

I. Air–Water–Soil Interactions 359II. Total Body Burden 365III. The Human Respiratory System 378IV. Impact of Air Pollution on Humans 381V. Impact of Odor on Humans 394


12 Effects on Vegetation and Animals

I. Injury versus Damage 397II. Effects on Vegetation and Crops 399III. Effects on Forests 403IV. Effects on Animals 408References 411Suggested Reading 412Questions 412

13 Effects on Materials and Structures

I. Effects on Metals 413II. Effects on Stone 416III. Effects on Fabrics and Dyes 417IV. Effects on Leather, Paper, Paint, and Glass 419V. Effects on Rubber 420


x Contents

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14 Effects on the Atmosphere, Soil, and Water Bodies

I. The Physics of Visibility 423II. Formation of Atmospheric Haze 430

III. Effects of Atmospheric Haze 433IV. Visibility 434V. Acidic Deposition 435

VI. Effects of Acidic Deposition 438References 439Suggested Reading 440Questions 441

15 Long-Term Effects on the Planet

I. Global Climate Change 442II. Ozone Holes 451References 453Suggested Reading 454Questions 454

Part IV

The Measurement and Monitoring of Air Pollution

16 Ambient Air Sampling

I. Elements of a Sampling System 457II. Sampling Systems for Gaseous Pollutants 459

III. Sampling Systems for Particulate Pollutants 463IV. Passive Sampling Systems 466V. Sampler Siting Requirements 468

VI. Sampling for Air Toxics 469References 470Suggested Reading 470Questions 470

17 Ambient Air Pollutants: Analysis and Measurement

I. Analysis and Measurement of Gaseous Pollutants 472II. Analysis and Measurement of Particulate Pollutants 487

III. Analysis and Measurement of Odors 490IV. Analysis and Measurement of Visibility 492V. Analysis and Measurement of Acidic Deposition 496


Contents xi

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18 Air Pollution Monitoring and Surveillance

I. Stationary Monitoring Networks 500II. Mobile Monitoring and Surveillance 503

III. Remote Sensing 505IV. Personal Monitoring 506V. Quality Assurance 508

VI. Data Analysis and Display 510References 513Suggested Reading 513Questions 513

19 Air Pathways from Hazardous Waste Sites

I. Introduction 515II. Multimedia Transport 516

III. Contaminant Fate Analysis 516IV. Modeling 524V. Assessment of a Hazardous Waste Site 525


Part V

Air Pollution Modeling

20 The Meteorological Bases of Atmospheric Pollution

I. Ventilation 537II. Stagnation 539III. Meteorological Conditions during Historic Pollution

Episodes 540IV. Effects of Pollution on the Atmosphere 546V. Removal Mechanisms 547


21 Transport and Dispersion of Air Pollutants

I. Wind Velocity 552II. Turbulence 554

III. Estimating Concentrations from Point Sources 557IV. Dispersion Instrumentation 566

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V. Atmospheric Tracers 571VI. Concentration Variation with Averaging Time 576References 578Suggested Reading 579Questions 579

22 Air Pollution Modeling and Prediction

I. Plume Rise 582II. Modeling Techniques 585

III. Modeling Nonreactive Pollutants 587IV. Modeling Pollutant Transformations 590V. Modeling Air Pollutants 593

VI. Model Performance, Accuracy, and Utilization 627References 633Suggested Reading 636Questions 637

23 Air Pollution Climatology

I. Sources of Data 638II. Representativeness 641

III. Frequency of Atmospheric Stagnations 646IV. Ventilation Climatology 647V. Wind and Pollution Roses 650


Part VI

The Regulatory Control of Air Pollution

24 Air Quality Criteria and Standards

I. Air Quality Criteria 659II. Conversion of Effects Data and Criteria to Standards 659

III. Conversion of Physical Data and Criteria to Standards 669IV. Conversion of Biological Data and Criteria to Standards 671V. Air Quality Standards 672

Suggested Reading 677Questions 678

25 Indoor Air Quality

I. Changing Times 679II. Factors Influencing Indoor Air Quality 680

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III. Indoor Air Pollutants 682IV. Effects of Indoor Air Pollutants 685V. Control of Indoor Air Pollutants 687


26 Regulating Air Pollution

I. Introduction 696II. Titles 697References 706Suggested Reading 706Questions 706

27 Emission Standards

I. Subjective Standards 707II. Objective Standards 709

III. Types of Emission Standards 713IV. Variant Forms of Emission Standards 713V. Means for Implementing Emission Standards 715


28 The Elements of Regulatory Control

I. Control of New Stationary Sources 724II. Control of Existing Stationary Sources 725

III. Control of Mobile Sources 726IV. Air Quality Control Regions 727V. Tall Stacks and Intermittent and Supplementary Control

Systems 728References 729Suggested Reading 729Questions 729

29 Organization for Air Pollution Control

I. Functions 730II. Organization 733

III. Finance 736IV. Advisory Groups 737Suggested Readings 738Questions 739

xiv Contents

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Part VII

Preventing and Controlling Air Pollution

30 Preventing Air Pollution

I. Introduction 743II. Sustainability 743

III. Green Engineering and Sustainability 744IV. Life Cycle Analysis 753V. Pollution Prevention 756

VI. Motivations for Practicing Green Engineering 761VII. Future People 767References 770Suggested Reading 772Questions 772

31 Engineering Control Concepts

I. Introduction 774II. Process Change 776

III. Fuel Change 777IV. Pollution Removal 778V. Disposal of Pollutants 780


32 Control Devices, Technologies, and Systems

I. Introduction 786II. Removal of Dry PM 794

III. Removal of Liquid Droplets and Mists 807IV. Removal of Gaseous Pollutants 810V. Removal of Odors 821


33 Control of Hazardous Air Pollutants

I. Air Quality and Hazardous Wastes 825II. Pre-control Considerations 830

III. Contaminant Treatment and Control Approaches 832IV. Thermal Treatment Processes 835V. Thermal Destruction Systems 839

Contents xv

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VI. Destruction Removal 844VII. Other Thermal Processes 845VIII. Indirect Air Impacts 848References 849Suggested Reading 850Questions 850

34 Control of Stationary Sources

I. Introduction 852II. Energy, Power, and Incineration 853

III. Chemical and Metallurgical Industries 859IV. Agriculture and Forest Products Industries 872V. Other Industrial Processes 878


35 Control of Mobile Sources

I. Introduction 886II. Gasoline-Powered Vehicles 886

III. Diesel-Powered Vehicles 889IV. Gas Turbines and Jet Engines 889V. Alternatives to Existing Mobile Sources 891


36 Source Sampling and Monitoring

I. Introduction 895II. Source Sampling 895

III. Statistics of Sampling 897IV. The Source Test 899V. Source Monitoring 910


37 The Future of Air Pollution

I. The Good News 917II. Stubborn Problems and Innovative Solutions 917

Index 919

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Preface to theThird Edition

The authors of this book include a chemist (Donald L. Fox), a meteorolo-gist (D. Bruce Turner), and a mechanical engineer (Richard W. Boubel). This1:1:1 ratio has some relevance in that it approximates the ratio of those pro-fessionally involved in the field of air pollution. In the environmental protec-tion and management field, the experience of the recent past has been thatphysicists and electrical engineers have been most attracted to the radiation,nuclear, and noise areas; biologists and civil engineers to the aquatic andsolid waste areas; chemists, meteorologists, and chemical and mechanicalengineers to the area of air pollution and its control. These remarks are notintended to exclude all others from the party (or from this course). The con-trol of air pollution requires the combined efforts of all the professions men-tioned, 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 itscontents and presentation.

Although this book consists of six parts and three authors, it is not to be con-sidered six short books put together back-to-back to make one large one. Byand large, the several parts are the work of more than one author. Obviously,the meteorologist member of the author team is principally responsible for thepart of the book concerned with the meteorology of air pollution, the chemistauthor for the chapters on chemistry, and the engineer author for those onengineering. However, as you will see, no chapters are signed, and all authors

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accept responsibility for the strengths and weaknesses of the chapters and forthe book as a whole.

In the 20 years since publication of the first edition of Fundamentals of AirPollution (1973), and the 9 years since the second edition (1984), the fundamen-tals have not changed. The basic physics, chemistry, and engineering are stillthe same, but there is now a greater in-depth understanding of their applica-tion to air pollution. This edition has been edited, revised, and updated toinclude the new technology available to air pollution practitioners. Its contentsare also influenced to a great extent by the passage of the US Clean Air ActAmendments of 1990 (CAAA90). These amendments have changed the healthand risk-based regulations of the US Clean Air Act to technology-driven regu-lations with extensive penalty provisions for noncompliance.

We have added more detailed discussion of areas that have been underintensive study during the past decade. There has been a similar need to adddiscussion of CAAA90 and its regulatory concepts, such as control of air tox-ics, indoor air pollution, pollution prevention, and trading and banking ofemission rights. Ten more years of new data on air quality have required theupdating of the tables and figures presenting these data.

We have expanded some subject areas, which previously were of concern toonly a few scientists, but which have been popularized by the media to the pointwhere 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 earlierdecades become obsolete and are replaced by processes and equipment thatproduce less pollution. At the same time, population and the demand forproducts and services increase. Students must keep these concepts in mindas they study from this text, knowing that the world in which they will prac-tice their profession will be different from the world today.

The viewpoint of this book is first that most of the students who elect toreceive some training in air pollution will have previously taken courses inchemistry at the high school or university level, and that those few who havenot would be well advised to defer the study of air pollution until they catchup on their chemistry.

The second point of view is that the engineering design of control systems forstationary and mobile sources requires a command of the principles of chemicaland mechanical engineering beyond that which can be included in a one-vol-ume textbook on air pollution. Before venturing into the field of engineeringcontrol of air pollution, a student should, as a minimum, master courses ininternal combustion engines, power plant engineering, the unit processes ofchemical engineering, engineering thermodynamics, and kinetics. However,this does not have to be accomplished before taking a course based on thisbook but can well be done simultaneously with or after doing so.

The third point of view is that no one, regardless of their professional back-ground, should be in the field of air pollution control unless they sufficiently

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understand the behavior of the atmosphere, which is the feature that differ-entiates air pollution from the other aspects of environmental protection andmanagement. This requires a knowledge of some basic atmospheric chem-istry in addition to some rather specialized air pollution meteorology. Theviewpoint presented in the textbook is that very few students using it willhave previously studied basic meteorology. It is hoped that exposure to airpollution meteorology at this stage will excite a handful of students to delvedeeper into the subject. Therefore, a relatively large proportion of this bookhas been devoted to meteorology because of its projected importance to thestudent.

The authors have tried to maintain a universal point of view so that thematerial presented would be equally applicable in all the countries of theworld. Although a deliberate attempt has been made to keep Americanprovincialism out of the book, it has inevitably crept in through the exclusiveuse of English language references and suggested reading lists, and the pre-ponderant use of American data for the examples, tables, and figures. Thesaving 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 profes-sional careers to the field of air pollution, the authors believe in its impor-tance and relevance. We believe that as the world’s population increases, itwill become increasingly important to have an adequate number of well-trained professions engaged in air pollution control. If we did not believethis, it would have been pointless for us to have written this textbook.

We recognize that, in terms of short-term urgency, many nations and com-munities may rightly assign a lower priority to air pollution control than toproblems of population, poverty, nutrition, housing, education, water sup-ply, communicable disease control, civil rights, mental health, aging, orcrime. Air pollution control is more likely to have a higher priority for a per-son or a community already reaping the benefits of society in the form ofadequate income, food, housing, education, and health care than for personswho have not and may never reap these benefits.

However, in terms of long-term needs, nations and communities canignore air pollution control only at their peril. A population can subsist, albeitpoorly, with inadequate housing, schools, police, and care of the ill, insane,and aged; it can also subsist with a primitive water supply. The ultimatedeterminants for survival are its food and air supplies. Conversely, evenwere society to succeed in providing in a completely adequate manner all ofits other needs, it would be of no avail if the result were an atmosphere sobefouled as not to sustain life. The long-term objective of air pollution con-trol 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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Preface to theFourth Edition

In the Preface to the Third Edition of this book, Donald L. Fox, D. BruceTurner, and Richard W. Boubel expressed the importance of a multidiscipli-nary approach to air pollution. I wholeheartedly agree. Nothing haschanged in this regard, making it a daunting challenge to update the impres-sive work of these renowned experts (as well as the late Arthur C. Stern inprevious editions). It was easier to add new material than to remove oldmaterial. A new edition is an optimization exercise. The book must notchange so much that professors using it have to change the course structureso severely that it constitutes a completely new text. On the other hand, atext must be up to date in terms of current technologies and programs, aswell as in addressing threats on the horizon.

Over a decade has passed since the publication of previous version. From aregulatory perspective, this is a very long time. By conventional measures, suchas the National Ambient Air Quality Standards, the past decade has been verysuccessful. But, science marches on. I recall that in the 1970s, detection in theparts per million (ppm) was impossible for most compounds. During the 1980sdetection limits continued to decrease. Now, detections have improved to allowfor measurements below parts per billion for many compounds. We have alsowitnessed sea changes in risk assessment and management. For example, theUS Environmental Protection Agency laboratories were realigned to addressrisks, with separate laboratories to conduct research exposure, effects, risk char-acterization, and risk reduction.

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Indeed, the previous authors were quite prescient in predicting the effectsof the then newly amended Clean Air Act. The major changes started to kickin as the focus moved from technology-based approaches (best available andmaximum 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 physicaland chemical processes at work, particularly those related to air toxics. Thishas been a tendency through all four editions. New technologies must beexplained, better models and computational methods have become available,analytical procedures have evolved and improved, and acute and chroniceffects have become better understood. All of these have enhanced the scienceand engineering knowledge available to practitioners, teachers, and students.And, the savvy of the lay public about air pollution has grown substantiallyduring the previous decade.

I am indebted to my fellow scientists and engineers for their insights andcomments on how to incorporate the new trends. I particularly want to noteAlan Huber, who shared his work in atmospheric dispersion modeling,especially computational fluid dynamics. Others include Russ Bullock (mer-cury 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 receivedsome formal background in chemistry. I agree with the previous authors thatanyone interested in air pollution must have a solid grounding in chemistryand 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 goodintentions. But, so-called “advocacy” does not obviate the need for sound sci-ence. That said, with a bit of effort, much of this edition can be a useful toolto any audience who is motivated to understand the what, how and why ofair pollution.

Another trend that I have hoped to capture is the comprehensivenessneeded to address air quality. A problem need not occur if the processesleading to air pollution are approached from a life cycle or “green” perspec-tive. This goes beyond pollution prevention and calls for an integrated andsustainable view. I have dedicated an entire chapter to this emergent envi-ronmental expectation.

The authors of the previous edition introduced discussions about someemerging continental and global threats to the atmosphere. Since then, the urgency of some has abated (e.g. acid rain and some threats to the ozonelayer), some have increased in concern (e.g. global warming), and othershave continued but the contaminants of concern have varied (long-rangetransport of persistent chemicals). The scientific credibility of arguments

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for and against regulatory and other actions has been uneven. The bestdefense against bad policy decisions is a strong foundation in the physicalsciences.

Let me rephrase that a bit more proactively and optimistically:

My overall objective of this book is to give you, the reader, theability to design and apply the tools needed to improve and sustainthe quality of the air we breathe for many decades. These tools canonly be trusted if they are thoroughly grounded in the Fundamentalsof Air Pollution.

DAV

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