Hazardous Air Pollutant Handbook: Measurements, Properties, and Fate in Ambient Air

242 Pages·2002·3.31 MB·English

by  Chester W. Spicer

HAZARDOUS
AIR POLLUTA NT
H A NDBOOK
Measurements,
Properties,
and Fate
in Ambient Air
L1571_fm_frame Page 2 Monday, March 4, 2002 2:30 PM
H AZA RDOUS
A IR POLLUTA NT
H A NDBOOK
Measurements,
Properties,
and Fate
in Ambient Air
Chester W. Spicer
Sydney M. Gordon
Michael W. Holdren
Thomas J. Kelly
R. Mukund
LEWIS PUBLISHERS
A CRC Press Company
Boca Raton London New York Washington, D.C.
L1571_fm_frame Page 4 Monday, March 4, 2002 2:30 PM
Library of Congress Cataloging-in-Publication Data
Hazardous air pollutant handbook : measurements, properties, and fate in ambient air /
Chester W. Spicer … [et al].
p. cm.
Includes bibliographical references and index.
ISBN 1-56670-571-1 (alk. paper)
1. Air—Pollution--Handbooks, manuals, etc. 2. Pollutants--Handbooks, manuals, etc. I.
Spicer, Chester W.
TD883 .H396 2002
628.5‘—dc21 2002017540
This book contains information obtained from authentic and highly regarded sources. Reprinted material is quoted with
permission, and sources are indicated. A wide variety of references are listed. Reasonable efforts have been made to publish
reliable data and information, but the author and the publisher cannot assume responsibility for the validity of all materials
or for the consequences of their use.
Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical,
including photocopying, microfilming, and recording, or by any information storage or retrieval system, without prior
permission in writing from the publisher.
All rights reserved. Authorization to photocopy items for internal or personal use, or the personal or internal use of specific
clients, may be granted by CRC Press LLC, provided that $.50 per page photocopied is paid directly to Copyright clearance
Center, 222 Rosewood Drive, Danvers, MA 01923 USA. The fee code for users of the Transactional Reporting Service is
ISBN 1-56670-571-1/02/$0.00+$.50. The fee is subject to change without notice. For organizations that have been granted
a photocopy license by the CCC, a separate system of payment has been arranged.
The consent of CRC Press LLC does not extend to copying for general distribution, for promotion, for creating new works,
or for resale. Specific permission must be obtained in writing from CRC Press LLC for such copying.
Direct all inquiries to CRC Press LLC, 2000 N.W. Corporate Blvd., Boca Raton, Florida 33431.
Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for
identification and explanation, without intent to infringe.
Visit the CRC Press Web site at www.crcpress.com
© 2002 by CRC Press LLC
Lewis Publishers is an imprint of CRC Press LLC
No claim to original U.S. Government works
International Standard Book Number 1-56670-571-1
Library of Congress Card Number 2002017540
Printed in the United States of America 1 2 3 4 5 6 7 8 9 0
Printed on acid-free paper
L1571_fm_frame Page 5 Monday, March 4, 2002 2:30 PM
Acknowledgments
The authors would like to thank the numerous people who have contributed to this effort. Battelle
colleagues Al Pollack, Melinda Armbruster, and Susan Abbgy participated in the literature surveys,
and Leanna House and Steve Bortnick contributed to the update of the ambient concentration
survey. We are indebted to the U.S. Environmental Protection Agency and Drs. Larry Cupitt, William
McClenny, and Robert Lewis for support and advice. We also wish to acknowledge the Atmospheric
Science and Applied Technology Department of Battelle for providing secretarial support and other
resources during the production of this handbook, and Mary Ann Roberts for assistance with
manuscript preparation.
L1571_fm_frame Page 6 Monday, March 4, 2002 2:30 PM
L1571_fm_frame Page 7 Monday, March 4, 2002 2:30 PM
The Authors
Chester W. Spicer is a senior research leader in the Atmospheric Science and Applied Technology
Department of Battelle in Columbus, OH. His academic background includes a B.A. in chemistry
from Rutgers University and a Ph.D. in analytical chemistry from Pennsylvania State University.
His principal interests and activities include the elucidation of atmospheric chemical transforma-
tions, studies of the distribution and fate of hazardous air pollutants, indoor and outdoor air quality
and development of analytical methods for gas and aerosol measurement. He has directed numerous
scientific investigations utilizing research aircraft, mobile laboratories, research houses and smog
chambers.
Dr. Spicer’s recent research includes studies of urban photochemical air pollution through
monitoring from aircraft and skyscrapers, studies of gaseous halogen contributions to ozone deple-
tion in the Arctic, the identification and sources of molecular halogens in the marine atmosphere,
chemical transformations of oxidized nitrogen compounds in indoor environments, the sources and
variability of hazardous air pollutants in urban areas, and emissions of toxic pollutants from diverse
sources including aircraft engines, natural gas appliances and military munitions.
He is past chairman of the Editorial Review Board of the Air and Waste Management Associ-
ation, and has served on the Editorial Board of the Journal of Environmental Forensics. He recently
served on the National Academy of Sciences/National Research Council Panel on Atmospheric
Effects of Aviation. Dr. Spicer is a member of the American Geophysical Union, the American
Chemical Society, the American Association for the Advancement of Science, the Air and Waste
Management Association and the International Society of Indoor Air Quality and Climate.
Sydney M. Gordon is a research leader in the Atmospheric Science and Applied Technology
Department of Battelle in Columbus. His research focuses on the development and application of
methods for measuring trace-level pollutants in ambient and indoor air. The characterization of
pollutants in human exhaled breath is a particular area of interest for application in human exposure
assessments.
At Battelle, Dr. Gordon leads a human exposure assessment group that concentrates on large
multipollutant, multimedia studies, and manages a variety of programs funded by government and
industrial clients. Much of his recent work has dealt with the development of new mass spectrometric
techniques for use in environmental and biomedical problems. He is the author or co-author of
more than 120 research publications, book chapters, and presentations.
Dr. Gordon received his D.Sc. in physical chemistry from the University of Pretoria, South
Africa, in 1965. He is a member of the American Chemical Society, the International Society of
Exposure Analysis, and the American Society for Mass Spectrometry. He is listed in American
Men and Women of Science, Who’s Who in the Midwest, and Who’s Who in America.
Michael W. Holdren is a senior research scientist in the Atmospheric Science and Applied Tech-
nology Department of Battelle in Columbus. His academic background includes a B.S. in chemistry
from Washington State University and an M.S. in Environmental Engineering (Air Pollution Stud-
ies) from Washington State University. His main interests include determination of human exposure
to environmental pollutants, development of sampling and analytical methodologies for measuring
air toxics, and investigations of atmospheric chemistry processes — chemical transformation and
chemical and physical removal in indoor and outdoor environments.
L1571_fm_frame Page 8 Monday, March 4, 2002 2:30 PM
Mr. Holdren has been actively involved with the U.S. EPA and Department of Defense in
developing gas chromatography/mass spectrometric techniques for measuring toxic air pollutants.
He has provided technical input and review on many of the U.S. EPA Toxic Organic (TO) docu-
ments. He is a co-author of the TO-15 document, which provides guidance for sampling and
analyzing the volatile hazardous air pollutants (HAPs) listed in Title III of the 1990 Clean Air Act
Amendments (CAAA). He is also working closely with industry in complying with the HAPs
emission requirements of the 1990 CAAA. Most of this industrial work focuses on determining
air emission factors for chemical processes and consumer products.
He is a member of several professional societies that include the Air and Waste Management
Association, Phi Kappa Phi, and Toastmasters International.
Thomas J. Kelly is a senior research scientist in the Atmospheric Science and Applied Technology
Department of Battelle in Columbus. He received a B.S. in chemistry from Michigan State Uni-
versity and a Ph.D. in analytical chemistry from the University of Michigan. His research interests
include the development and evaluation of analytical methods for environmental pollutants and
natural trace species, and the use of monitoring data to determine sources and assess human
exposures to airborne pollutants. He has conducted air sampling programs in residential buildings,
at industrial facilities, at surface sites, and aboard aircraft; performed data reviews and modeling
related to atmospheric chemistry and deposition; and carried out source apportionment of particle-
and vapor-phase air pollutants.
Dr. Kelly is the verification testing leader in Battelle’s Advanced Monitoring Systems Center,
which is part of the U.S. EPA’s Environmental Technology Verification (ETV) program. In that
capacity he plans, organizes, conducts, and reports on performance evaluations of environmental
monitoring technologies. Recent subjects of ETV testing include continuous emission monitors for
mercury, and continuous monitors for mass and composition of fine particles in the atmosphere.
His other recent activities include development of a real-time monitor for nitrogen dioxide and
nitrous acid in indoor air, determination of particle and gas emissions from residential cooking
activities, and determination of chemical emission rates from consumer products. He holds two
patents on air monitoring devices.
R. Mukund is manager, E-Business and Compliance Systems for General Electric Corporate
Environmental Programs. He is currently based in Cincinnati. He received his M.Sc. in Chemistry
from the Indian Institute of Technology, Kanpur, and his M.S. and Ph.D. in Environmental Science
in Civil Engineering from the University of Illinois, Urbana-Champaign. His current focus is on
the development and implementation of Web-based management systems for environmental, health
and safety (EHS) processes at global manufacturing and service operations. He is also involved in
compliance assurance processes, including facility based self-assessment programs, as well as
business and corporate audit programs.
Previously, Dr. Mukund led air compliance management and EHS compliance assurance pro-
grams for GE’s Power Systems business in Schenectady, NY, and earlier provided Title V air
permitting and consulting services for government and industrial clients at ERM-Northeast in
Albany, NY.
Prior to his more recent work in environmental consulting and corporate EHS management,
Dr. Mukund was part of the Battelle research team that conducted a series of studies relating to
hazardous air pollutants, including surveys of ambient air measurement methods, chemical mass
balance modeling of the sources of HAPs in urban air, and dispersion modeling studies.
Dr. Mukund is a member of the Air and Waste Management Association.
L1571_fm_frame Page 9 Monday, March 4, 2002 2:30 PM
Table of Contents
Chapter 1
Hazardous Air Pollutants: A Brief Introduction
1.1 Background...............................................................................................................................1
1.2 The List of Hazardous Air Pollutants......................................................................................2
1.3 Impact of the HAPs List..........................................................................................................8
1.4 Organization of Information in this Book...............................................................................9
References........................................................................................................................................10
Chapter 2
The Title III Hazardous Air Pollutants: Classification and Basic Properties
2.1 The 188 Hazardous Air Pollutants: Diversity and Derivation...............................................11
2.2 Some Common Features of the Title III HAPs.....................................................................11
2.3 Chemical and Physical Properties of the 188 HAPS............................................................12
2.4 Polarizability and Water Solubility as Defining Characteristics of Polar and
Nonpolar VOCs......................................................................................................................13
Appendix..........................................................................................................................................23
Chapter 3
Measurement Methods for the 188 Hazardous Air Pollutants in Ambient Air
3.1 Introduction.............................................................................................................................55
3.2 Background.............................................................................................................................56
3.3 Survey Approach....................................................................................................................57
3.4 Status of Current Methods.....................................................................................................59
3.5 HAPs Method Development: Future Directions....................................................................60
3.6 Summary.................................................................................................................................62
References........................................................................................................................................62
Appendix..........................................................................................................................................65
Chapter 4
Concentrations of the 188 HAPs in Ambient Air
4.1 Introduction...........................................................................................................................127
4.2 Survey Procedures................................................................................................................127
4.3 Ambient Air Concentrations of HAPs.................................................................................129
4.4 Data Gaps.............................................................................................................................131
4.5 Recent Data for High Priority HAPs...................................................................................134
4.6 Summary...............................................................................................................................134
References......................................................................................................................................134
Appendix........................................................................................................................................136