Urban Aerosols and Their Impacts: Lessons Learned from the World Trade Center Tragedy 0841239169, 9780841239166

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ACS SYMPOSIUM SERIES

919

Urban Aerosols and Their Impacts Lessons Learned from the World Trade Center Tragedy

Jeffrey S. Gaffney, Editor Argonne National Laboratory

Nancy A. Marley, Editor Argonne National Laboratory

Sponsored by the

ACS Divisions of Environmental Chemistry, Inc. and Geochemistry, Inc.

American Chemical Society, Washington, DC

Library of Congress Cataloging-in-Publication Data Urban aerosols and their impacts : lessons learnedfromthe World Trade Center Tragedy / Jeffrey S. Gaffney, editor; Nancy A. Marley, editor; sponsored by the ACS Divisions of Environmental Chemistry, Inc. and Geochemistry, Inc. p. cm. — (ACS symposium series ; 919) "Developedfroma symposium sponsored by the Divisions of Environmental Chemistry, Inc. and Geochemistry, Inc. at the 226 National Meeting of the American Chemical Society, New York, September 7-11,2003"—Pref. th

Includes bibliographical references and index. ISBN-13: 978-0-8412-3916-6 (alk. paper) 1. Dust—Environmental aspects—Congresses. 2. Aerosols—Environmental aspects—Congresses 3. Air—Pollution—Congresses. 4. Construction and demolition debris—Environmental aspects—New York (State)—New York—Congresses. 5. World Trade Center Site (New York, N.Y.)—Congresses. I. American Chemical Society. Divisions of Environmental Chemistry, Inc. and Geochemistry, Inc.. II. American Chemical Society. Meeting (226 : 2003 : New York, N.Y.). III. Series. th

TD884.5.U93 2005 628.5'3-dc22 2005048306 The paper used in this publication meets the minimum requirements of American National Standard for Information Sciences—Permanence of Paper for Printed Library Materials, ANSI Z39.48-1984. Copyright © 2006 American Chemical Society Distributed by Oxford University Press ISBN 10: 0-8412-3916-9 All Rights Reserved. Reprographic copying beyond that permitted by Sections 107 or 108 of the U.S. Copyright Act is allowed for internal use only, provided that a per-chapter fee of $30.00 plus $0.75 per page is paid to the Copyright Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. Republication or reproduction for sale of pages in this book is permitted only under licensefromACS. Direct these and other permission requests to ACS Copyright Office, Publications Division, 1155 16th Street, N.W., Washington, DC 20036. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by ACS of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of anyrightor permission to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN THE UNITED STATES OF AMERICA

Foreword The ACS Symposium Series was first published in 1974 to provide a mechanism for publishing symposia quickly in book form. The purpose of the series is to publish timely, comprehensive books developed from ACS sponsored symposia based on current scientific research. Occasionally, books are developedfromsymposia sponsored by other organizations when the topic is of keen interest to the chemistry audience. Before agreeing to publish a book, the proposed table of contents is reviewed for appropriate and comprehensive coverage and for interest to the audience. Some papers may be excluded to better focus the book; others may be added to provide comprehensiveness. When appropriate, overview or introductory chapters are added. Drafts of chapters are peer-reviewed prior to final acceptance or rejection, and manuscripts are prepared in camera-ready format. As a rule, only original research papers and original review papers are included in the volumes. Verbatim reproductions of previously published papers are not accepted.

ACS Books Department

Table of Contents Preface JEFFREY S. GAFFNEY and NANCY A. MARLEY

ix-xv

Overview 1 Introduction to Urban Aerosols and Their Impacts Nancy A. Marley and Jeffrey S. Gaffney

2-22

2 An Overview of the Environmental Conditions and Human Exposures That Occurred Post September 11, 2001 Paul J. Lioy, Panos G. Georgopoulos, and Clifford P. Weisel 23-38

World Trade Center Dust Characterization 3 Spectroscopic and X-ray Diffraction Analyses of Asbestos in the World Trade Center Dust: Asbestos Content of the Settled Dust Gregg A. Swayze, Roger N. Clark, Stephen J. Sutley, Todd M. Hoefen, Geoffrey S. Plumlee, Gregory P. Meeker, Isabelle K. Brownfield, K. Eric Livo, and Laurie C. Morath 40-65 4 Environmental Mapping of the World Trade Center Area with Imaging Spectroscopy after the September 11,2001 Attack - The Airborne Visible/Infrared Imaging Spectrometer Mapping Roger N. Clark, Gregg A. Swayze, Todd M. Hoefen, Robert O. Green, K. Eric Livo, Gregory P. Meeker, Stephen J. Sutley, Geoffrey S. Plumlee, Betina Pavri, Chuck Sarture, Joe Boardman, Isabelle K. Brownfield, and Laurie C. Morath 66-83 5 Materials Characterization of Dusts Generated by the Collapse of the World Trade Center Gregory P. Meeker, Stephen J. Sutley, Isabelle K. Brownfield, Heather A. Lowers, Amy M. Bern, Gregg A. Swayze, Todd M. Hoefen, Geoffrey S. Plumlee, Roger N. Clark, and Carol A. Gent 84-102 6 Persistent Organic Pollutants in Dusts That Settled at Indoor and Outdoor Locations in Lower Manhattan after September 11, 2001 John H. Offenberg, Steven J. Eisenreich, Cari L. Gigliotti, Lung Chi Chen, Mitch D. Cohen, Glenn R. Chee, Colette M. Prophete, Judy Q. Xiong, Chunli Quan, Xiaopeng Lou, Mianhua Zhong, John Gorczynski, Lih-Ming Yiin, Vito Illacqua, Clifford P. Weisel, and Paul J. Lioy 103-113 7 Characterization of Size-Fractionated World Trade Center Dust and Estimation of Relative Dust Contribution to Ambient Particulate Concentrations Polina B. Maciejczyk, Rolf L. Zeisler, Jing-Shiang Hwang, George D. Thurston, and Lung Chi Chen 114-131

World Trade Center Fine Particle and Volatile Organic Emissions 8 Characterization of the Plumes Passing over Lower Manhattan after the World Trade Center Disaster Robert Z. Leifer, Graham S. Bench, and Thomas A. Cahill 135-151 9 Very Fine Aerosols from the World Trade Center Collapse Piles: Anaerobic Incineration? Thomas A. Cahill, Steven S. Cliff, James F. Shackelford, Michael L. Meier, Michael R. Dunlap, Kevin D. Perry, Graham S. Bench, and Robert Z. Leifer 152-163 10 Semivolatile Organic Acids and Levoglucosan in New York City Air Following September 11, 2001 Michael D. Hays, Leonard Stockburger, John D. Lee, Alan F. Vette, and Erick C. Swartz 164-188

World Trade Center Exposure Assessments 11 Evaluation of Potential Human Exposures to Airborne Particulate Matter Following the Collapse of the World Trade Center Towers Joseph P. Pinto, Lester D. Grant, Alan F. Vette, and Alan H. Huber 190-237 12 Inorganic Chemical Composition and Chemical Reactivity of Settled Dust Generated by the World Trade Center Building Collapse Geoffrey S. Plumlee, Philip L. Hageman, Paul J. Lamothe, Thomas L. Ziegler, Gregory P. Meeker, Peter M. Theodorakos, Isabelle K. Brownfield, Monique G. Adams, Gregg A. Swayze, Todd M. Hoefen, Joseph E. Taggar, Roger N. Clark, Stephen E. Wilson, and Stephen J. Sutley 238-276 13 World Trade Center Environmental Contaminant Database: A Publicly Available Air Quality Dataset for the New York City Area Steven N. Chillrud, Alison S. Geyh, Diane K. Levy, Elsie M. Chettiar, and Damon A. Chaky 277-284

Aerosol Transport Issues 14 The Importance of the Chemical and Physical Properties of Aerosols in Determining Their Transport and Residence Times in the Troposphere Jeffrey S. Gaffney and Nancy A. Marley 286-299 15 210Po/210Pb in Outdoor—Indoor PM-2.5, and PM-1.0 in Prague, Wintertime 2003 Jan Hovorka, Robert F. Holub, Martin Braniš, and Bruce D. Honeyman 300-307 16 Estimates of the Vertical Transport of Urban Aerosol Particles Edward E. Hindman

308-320

Indexes Author Index

323-324

Subject Index

325-335

Color Figure Inserts

CI1-CI32

Preface Urban aerosols (fine airborne particulate matter) have received considerable attention because of their links with increased urban hospitalizations from chronic pulmonary and cardiac diseases, as well as increased daily mortality (1, 2). The terrorist attack on the World Trade Center (WTC) on September 11, 2001, and the subsequent tragic collapse of the twin towers resulted in unprecedented release and dispersal of potentially toxic gaseous and particulate materials in a cloud of dust and smoke that extended over lower Manhattan and other parts of New York City. A number of studies by both university and government researchers were undertaken immediately to evaluate the potential human health effects of exposure to the materials from the initial event and also from continued releases from smoldering fires and site cleanup that continued through mid December 2001. Evaluation of firefighters, cleanup workers, and community residents showed exposure-related increases in cough and bronchial hyperreactivity, while a follow-up of 182 pregnant women who were either inside or near the WTC on September 11 showed a twofold increase in smallfor-gestational-age infants (3). A symposium was held in New York City in September 2003 at the 226th National Meeting of the American Chemical Society (ACS), to present the findings of studies related to the WTC tragedy and to bring attention to the need for a better understanding of the chemical and physical properties of urban aerosols and their impacts. Papers were presented that described studies at the WTC site, including detailed characterizations of the particulate matter generated by the collapse, the potential health impacts of exposure, and the relationships between this single catastrophic event and everyday exposures to particulate matter in urban centers. This symposium brought together researchers from government, universities, and research institutions with the common goal of determining the type and extent of the exposures and the possible future impacts to the exposed population This book is a result of that symposium. Much of the work presented at the ACS meeting is included in the following chapters. In the interest of completeness, other work presented at the symposium but not included in detail in this volume is summarized in this Preface, along with other findings reported since September 2003.

© 2006 University of Chicago

ix

Several studies were conducted by researchers at the New York University School of Medicine at a site located at the New York University Downtown Hospital (NYUDH), about four blocks east of the WTC disaster site known as "Ground Zero." Samples were collected from September 14 to December 27, 2001. During this period, intense fires were burning at Ground Zero, and early cleanup efforts were taking place. The total mass concentrations of particulates < 15 µm ranged from 4.4 µg/m to 22.7 µg/m (4). None of the daily mass concentrations measured at the site exceeded the 24-h limit of 65 µg/m set by the U.S. Environmental Protection Agency (EPA) for particulate matter < 2.5 µm (PM-2.5). Bimodal mass concentration distributions showed one peak at a diameter of about 1.8 µm and a larger mode at 0.56 µm. Bimodal size distributions were also observed for several elements. Sulfur, which is typically found in atmospheric aerosols < 1.0µm,was present in sizefractionsboth above and below 1.0 µm Calcium was predominant in the larger particulates (> 1.0 µm) and correlated well with sulfur in this size range, suggesting that gypsum board containing calcium sulfate was a source. Vanadium was found primarily in the submicron sizefraction,indicating oil combustion as the main source. Particles collected at the NYUDH site exhibited a variety of globular forms, with most appearing to be agglomerates (5). No ultrafine acid particulates were detected. Hourly average aerosol number concentrations were variable, with occasionally very high, brief peaks reaching values over 7 x 10 cm . The average total aerosol mass concentration of 17 µg/m at this site in mid October decreased to roughly half that value in November and to as little as 5µg/m in mid December. Since the particle size distributions were mostly bimodal, the decrease in total mass was due mainly to a decrease in the large-particle fraction. The mass concentrations of very fine particles ranged from 4.3 µg/m to 0.7 µg/m , and the mass concentrations of ultrafine particulates ( 0.001 cm /sec (Figure 1), and therefore they can diffuse rapidly to the surfaces of other particles (5). In addition, these ultrafine aerosols can act as nuclei for the condensation of low-vapor-pressure gases causing them to grow rapidly into the next size range. Atmospheric aerosols in the coarse range, larger than approximately 2 |nm, are usually produced by mechanical processes such as grinding or wind erosion. Thus, because of the nature of their sources, they are composed predominately of minerals and inorganics such as sand and sea salt. Also included in this size range are larger bioaerosols such as spores, pollen, and bacteria. With settling velocities >0.01 cm/sec (see Figure 1), coarse aerosols are generally removed from the atmosphere fairly rapidly by sedimentation. However, the atmospheric transport of coarse aerosols can occur over relatively long distances by convective processes where fallout is balanced by reentrainment. Mineral dusts from western China have been detected in western North America (6) and Canada (7), and African mineral dusts have been detected in south central Florida (8). Aerosols in the intermediate size range from approximately 0.1-2 \im are known as the accumulation range. They are so named because the particle removal mechanisms of sedimentation and diffusion to surfaces are least effective in this range causing particles of this size to accumulate in the atmosphere. Aerosols in thisfinesize range typically arise from coagulation of 2

2

Diffusion Coefficient (cm /sec)

Settling Velocity (cm/sec)

Aerosol Mode

Electromagnetic Waves

Diameter (urn)

IO-

1

2

10-

Xrays

0.001 UV

0.1

4

io-

io1(H

101-2 7

10"

Bacteria

10

m

Hair

Pollen

Clouds & Fcfg

Fine Si nd

IR

100

Figure 1. Characteristics of atmospheric aerosols.

10-

Viruses

Fly Ash Sea Spray

MR

10

V find Blown D ust

Visible

Smoke

Combi stion Nuclei

>rbonBkck

Aitcen

0.01

«

1000 fl mm)

Rain

5 smaller particles in the Aitken range orfromcondensation of low-volatility gases (water vapor, organics, etc.) onto existing particles. Because of their sources, particles in the accumulation range typically contain organic compounds and soluble inorganics such as ammonium (NH4*), nitrate ( N 0 ) , and sulfate (S0 ~). Being too small to settle out of the atmosphere, they are removed relatively slowly, primarily by incorporation into clouds and subsequent rainout. The rate of cloud droplet formation from these aerosols depends on their chemical compositions and their hygroscopicity, with the more soluble species being removed faster. Alternately, fine aerosols can be removedfromthe atmosphere by dry deposition after being carried to surfaces by eddy diffusion (9). The properties of atmospheric aerosols that are important in determining their impacts to the environment and human health include their number concentration, mass, size, chemical composition, phase (liquid or solid), morphology, and surface properties. Currently, the U.S. Environmental Protection Agency (EPA) has two standards for particulate matter (aerosols) that are based on mass loadings. These are particulate matter