ENVIRONMENT Aerosol CHEMICAL PROCESSES IN THE © 2000 by CRC Press LLC Edited by Kvetoslav R. Spurny Special Editorial Consultant Dieter Hochrainer LEWIS PUBLISHERS Boca Raton London New York Washington, D.C. ENVIRONMENT Aerosol CHEMICAL PROCESSES IN THE © 2000 by CRC Press LLC 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. 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Trademark Notice: Product or corporate names may be trademarks or registered trademarks, and are used only for identification and explanation, without intent to infringe. © 2000 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 0-87371-829-1 Library of Congress Card Number 99-089288 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Library of Congress Cataloging-in-Publication Data Aerosol chemical processes in the environment/ K.R. Spurny, editor. p. cm. Includes bibliographical references and index. ISBN 0-87371-829-1 (alk. paper) 1. Aerosols Environmental aspects. I. Spurny, Kvetoslav. QC882.42.A32 2000 541 .3′ .4515—dc21 99-089288 CIP L829/frame/FM Page iv Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Dedication and Acknowledgment This volume is dedicated to its editor, Kvetoslav R. Spurny, whose untimely death on November 3, 1999 shocked and saddened all associ- ated with its publication. CRC Press/Lewis Publishers is privileged to have had a long-stand- ing relationship with Dr. Spurny, whose deep interest in science, drive to initiate and complete tasks, and kind personality are as integral to his publishing file as the tangible documents therein. The Publisher sin- cerely regrets that aerosol science has lost one of its founding fathers, a great scientist, and a renowned contributor to the literature in this field. Furthermore, the Publisher gratefully acknowledges Dr. Dieter Hochrainer of Boehringer Ingelheim, Dr. Spurny's former colleague at the Fraunhofer Institute, for his assistance in the final production of this book. L829/frame/FM Page v Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Acknowledgments The editor is extremely grateful to the authors for their excellent contributions. They have not only contributed to broader information on the progress, state of the art, and new concepts in the field of aerosol chemical processes, but they also have recognized the need for a monograph in aerosol chemistry. The editor would like to thank the staff of Lewis Publishers, a division of CRC Press LLC, for their substantial help with the realization of this book. The authors are globally distributed and, for the majority of them, English is not their mother tongue. Without the great, patient, and highly professional support of the publishers, the realization of this book would not have been possible. All — authors and publishers — have done an excellent job for aerosol science and aerosol scientists. L829/frame/FM Page vii Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Preface Aerosol science today is an interdisciplinary branch of science that incorporates several environ- mental, biological, and technological research fields. In a conference organized in Prague (Czech- oslovakia) in 1962, we were able to bring together lecturers from different scientific fields — physicists, chemists, meteorologists, biologists, physicians, hygienists, agrochemists, astrophysi- cists, etc. — and from several different countries. The conference showed the important role of aerosols and aerosol research in many basic and applied scientific and technological fields (Spurny, K., Ed ., Aerosols, Physical Chemistry and Applications , Academia Publ. House, Prague, 1965). Furthermore, the interdisciplinary cooperation was found to be very useful and necessary. I also remember the important role of chemistry in basic and applied aerosol research in a contri- bution, published in 1971 (Spurny, K.R., A note on the development of the chemistry of aerosols, J. Aerosol Sci., 2, 389, 1971). Now, being retired and 75 years old, I still feel that there is a need for more synthetic work in aerosol chemistry, consisting of summarizing and evaluating the very many aerosol chemical publications dispersed in the various journals among several disciplines. Nevertheless, such a task is not easily realized. It is perhaps beyond the feasibility of one or more editors to organize and compile a monograph like the Aerosol Chemistry Handbook , which would include and describe all or the most important aerosol chemical processes involved in already known scientific and technological areas. We consider this book a partial contribution to such a task. We have picked up several examples that show the impact of aerosol chemistry in several fields, mainly in basic and atmospheric research. American, European, and Japanese colleagues have substantially contributed to the realization of this book. I would like to thank them very much and hope their contributions will be helpful and useful to the readers. Kvetoslav R. Spurny L829/frame/FM Page ix Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Editor Prof. Dr. Kvetoslav R. Spurny was Head of the Department of Aerosol Chemistry at the Fraunhofer Institute for Environmental Chemistry and Ecotoxicology in Germany from 1972 to 1988. After his retirement, he continued to work as an aerosol chemist. Prior to this, he was an environmental chemist at the Institute for Occupational Hygiene in Prague (1952 to 1956) and Head of the Department of Aerosol Sciences at the Czechoslovak Academy of Sciences in Prague (1957 to 1972). He was a Visiting Scientist at the National Center for Atmospheric Research, Boulder, Colorado, (1966 to 1967) and Visiting Scientist at the Nuclear Research Center, Fontenay aux Roses, France, in 1969. Dr. Spurny obtained his diploma in Physics and Chemistry from Charles University, Prague, in 1948, a Ph.D. in chemistry at the same university in 1952, and a C.Sc. as a Candidate of Chemical Sciences at the Czechoslovak Academy of Sciences in Prague in 1964. Professor Spurny was a member of the American Chemical Society, American Association for the Advancement of Science, American Association of Aerosol Research, British Occupational Hygiene Society, the New York Academy of Sciences, and was president of the Association for Aerosol Research from 1983 to 1984. He wrote three books on aerosols and over 150 original publications in aerosol physics and chemistry. In 1989, he was the recipient of the American David Sinclair Award in Aerosol Sciences. L829/frame/FM Page xi Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Contributors Kai Bester Institute of Organic Chemistry Hamburg, Germany János Bobvos Municipal Institute of the State Public Health Officer Service Budapest, Hungary Mikhail V. Buikov Institute of Radioecology Ukrainian Academy of Agricultural Sciences Kiev, Ukraine Miroslav Chomát Institute of Radio Engineering and Electronics Academy of Sciences of the Czech Republic Prague, Czech Republic I. Colbeck Department of Biological Sciences University of Essex Colchester, U.K. Marco Del Monte Dipartamento di Scienze della Terra e Geologico-ambientali Bologna, Italy K. Hang Fung Department of Applied Science Brookhaven National Laboratory Upton, New York Mario Gallorini CNR Centro di Radiochimica e Analisi per Attivazione Universitá di Pavia Italy Alexandra Gogou Department of Chemistry Division of Environmental and Analytical Chemistry University of Crete Heraklion, Crete, Greece A. Hachimi Laboratoire de Spectrométrie de Masse et Chimie Laser IPEM Metz, France Heinrich Hühnerfuss Institute of Organic Chemistry University of Hamburg Hamburg, Germany Mark Z. Jacobson Department of Civil and Environmental Engineering Stanford University Stanford, California Satoshi Kadowaki Aichi Environmental Research Center Nagoya, Japan Ivan Kaˇsík Institute of Radio Engineering and Electronics Academy of Sciences of the Czech Republic Prague, Czech Republic G. Krier Laboratoire de Spectrométrie de Masse et Chimie Laser IPEM Metz, France Markku Kulmala Department of Physics University of Helsinki Helsinki, Finland Ari Laaksonen Department of Applied Physics University of Kuopio Kuopio, Finland Claude Landron Centre de Recherches sur les Matériaux à Haute Temperature Orléans, France L829/frame/FM Page xiii Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Willy Maenhaut University of Gent Gent, Belgium Vlastimil Matˇejec Institute of Radio Engineering and Electronics Academy of Sciences of the Czech Republic Prague, Czech Republic P. Mériaudeau CNRS Institut de Recherches sur la Catalyse Villeurbanne, France Javier Miranda Department of Experimental Physics Instituto de Física Universidad Nacional Autónoma de México México, D.F., Mexico J.F. Muller Laboratoire de Spectrométrie de Masse et Chimie Laser IPEM Metz, France Anders G. Nord National Heritage Board Satens Historska Museer Stockholm, Sweden S. Nyeki Department of Biological Sciences University of Essex Colchester, U.K. Vincent Perrichon LACE–CNRS Université Claude Bernard Villeurbanne, France E. Poitevin Laboratoire de Spectrométrie de Masse et Chimie Laser IPEM Metz, France Jan Rosinski Clouds and Precipitation Group Istituto delle Scienze dell´Atmosfera e dell´Oceano Bologna, Italy P. Rossi Agenzia Regionale Prevenzione e Ambiente Modena, Italy Glenn O. Rubel Department of the Army R&T Directorate SBCCOM-ECBC Aberdeen Proving Ground, Maryland Cristina Sabbioni CNR Instituto delle Scienze dell’Atmosfera e dell’Oceano Bologna, Italy Imre Salma KFKI Atomic Energy Research Institute Budapest, Hungary Kvetoslav R. Spurny Aerosol Chemist Schmallenberg, Germany Euripides G. Stephanou Department of Chemistry Environmental Chemical Processes Laboratory University of Crete Heraklion, Crete, Greece Ignatius N. Tang Department of Applied Science Brookhaven National Laboratory Upton, New York Timo Vesala Department of Physics University of Helsinki Helsinki, Finland Giuseppe Zappia CNR Scienze dei Materiali e della Terra Universitá di Ancona Ancona, Italy ´ Eva Zemplén-Papp Hungarian Academy of Sciences Budapest, Hungary L829/frame/FM Page xiv Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC Aerosol Chemistry WHAT IS AEROSOL CHEMISTRY DEALING WITH? An aerosol is a collection of fine and very fine particles dispersed in the gas phase. While aerosol physics tries to describe the mechanical and dynamical behavior of this system and the movement of particles in several force fields, and considers the single particle to be chemically inert, aerosol chemistry involves the physicochemical and chemical properties of the particles, in the chemical processes of particle generation, gas-to-particle and particle-to-particle reactions, interface interactions, and — on a large scale — the chemical effects of particles in several environmental fields and situations. Single aerosol particles are rarely inert; they are chemically varied and reactive. L829/frame/FM Page xv Wednesday, February 2, 2000 9:03 AM © 2000 by CRC Press LLC [...]... describe the formation of the SAAA and predict their behavior and characterization at urban and regional levels .11 The same is also valid for modeling the physical processes that are involved in model aerosol dynamics They are able to determine aerosol size distribution functions in correlation with time and space .17 The processes affecting aerosol behavior are summarized in the Table 1. 1 and Figure 1. 2 The. .. reduction in the fine particle fraction For example, the newer diesel engine (19 91) produces less mass of soot particles, but has increased emissions of ultrafine soot particles in comparison with the previous (19 88) diesel engine This could occur if the newer engine causes incomplete © 2000 by CRC Press LLC L829/frame/ch 01 Page 10 Monday, January 31, 2000 2:20 PM 10 Aerosol Chemical Processes in the Environment. .. consequently in uence the evolution of clouds, essentially all cloud properties are dependent on these aerosols In turn, clouds modify the preexisting aerosol, by removal and by aqueous reactions The ocean is the main source of hygroscopic CCN, through the bursting of bubbles in breaking waves Nevertheless, the continental air is also rich in natural and man-made CCN The importance of man-made CCN is increasing... measured in the damage layers of stone monuments in Rome (From Reference 84 With permission.) © 2000 by CRC Press LLC L829/frame/ch 01 Page 18 Monday, January 31, 2000 2:20 PM 18 Aerosol Chemical Processes in the Environment SAAA, mainly carbonaceous and metallic aerosols, are involved in the complex physicochemical and biological mechanisms that result in the deterioration and damages of stones and other inorganic... designated as the “respirable” or “thoracic” fraction and also as the PM -1 0 fraction It includes the “nucleation,” “accumulation,” and a portion of the “coarse” modes TSP (total suspended particles) is then designated as the fraction that includes the “nucleation,” “accumulation,” and “coarse” modes TSP and PM -1 0 were first introduced and standardized in 19 71. 21 The fractions PM-2.5 or PM -1 are now considered... America.6 0-6 5 The aerosols in the atmospheric environment of the forest are mainly imported into the forest areas from different industrial and automobile traffic emission sources However, they are also produced or modified by the vegetation inside the forest atmosphere The forest smog periods are well-known These are formed in the forest atmosphere by chemical and photochemical, as well as by gas-to-particle... metals are involved in microbial metabolism The capacity of foliage © 2000 by CRC Press LLC L829/frame/ch 01 Page 14 Monday, January 31, 2000 2:20 PM 14 FIGURE 1. 10 Aerosol Chemical Processes in the Environment Scanning electron micrographs of spruce needles and deposited mineral particles to accumulate trace-metal particles is considerable The metal cations interact with the microorganisms of the phyllosphere... Hygroscopic Aerosols 61 Ignatius N Tang Chapter 5 On the Role of Aerosol Particles in the Phase Transition in the Atmosphere 81 Jan Rosinski Chapter 6 Reversible Chemical Reactions in Aerosols 13 5 Mark Z Jacobson PART II LABORATORY STUDIES Chapter 7 LAMMA and Raman Study of Oxidation States of Chromium in Aerosols: Application to Industrial Hygiene 15 9 A Hachimi, E Poitevin,... troposphere J Geophys Res 10 1, 22, 869, 19 96 59 Schurath, U., Atmospheric aerosols: sources and sinks of reactive trace gases, J Aerosol Sci., 28, S 31, 19 97 60 Smith, W.H., Air Pollution and Forests, Spring Publishers, Heidelberg, Germany, 19 81 61 Spurny, K.R., Physico -chemical characterization of aerosols in a forest environment, J Aerosol Sci., 20, 11 03, 19 89 62 Mäkelä, J.M., Aalto, P., Jokinen, V et al.,... “bad” aerosols While the good aerosols are useful in their applications and effects, the bad aerosols produce negative, harmful effects on the environment and the human population Aerosol synthesis of nanoscale particles and powders belongs among the good aerosols These aerosol processes are currently used for the large-scale production of several modern materials, 1- 4 such as alumina, silica, carbon . Number 9 9-0 89288 Printed in the United States of America 1 2 3 4 5 6 7 8 9 0 Printed on acid-free paper Library of Congress Cataloging -in- Publication Data Aerosol chemical processes in the environment/ . Depletion 12 Aerosols in the Forest Atmosphere 13 “Forest Aerosol 13 Building Deterioration 15 References 18 INTRODUCTION Two kinds of aerosols can be distinguished: “good” aerosols and “bad” aerosols Hygroscopic Aerosols 61 Ignatius N. Tang Chapter 5 On the Role of Aerosol Particles in the Phase Transition in the Atmosphere 81 Jan Rosinski Chapter 6 Reversible Chemical Reactions in Aerosols