AEROSOL CHEMICAL PROCESSES IN THE ENVIRONMENT - CHAPTER 1 pot

The conference showed the important role ofaerosols and aerosol research in many basic and applied scientific and technological fields Spurny, Furthermore, the interdisciplinary cooperat

Aerosol CHEMICAL PROCESSES

I N T H E

Aerosol CHEMICAL PROCESSES

I N T H E

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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.

Dedication and Acknowledgment

This volume is dedicated to its editor, Kvetoslav R Spurny, whoseuntimely death on November 3, 1999 shocked and saddened all associ-ated with its publication

CRC Press/Lewis Publishers is privileged to have had a ing relationship with Dr Spurny, whose deep interest in science, drive

long-stand-to initiate and complete tasks, and kind personality are as integral long-stand-to hispublishing 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 DieterHochrainer of Boehringer Ingelheim, Dr Spurny's former colleague at theFraunhofer Institute, for his assistance in the final production of this book

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Aerosol science today is an interdisciplinary branch of science that incorporates several 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 ofaerosols and aerosol research in many basic and applied scientific and technological fields (Spurny,

Furthermore, the interdisciplinary cooperation was found to be very useful and necessary Ialso 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 needfor more synthetic work in aerosol chemistry, consisting of summarizing and evaluating the verymany 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

would include and describe all or the most important aerosol chemical processes involved in alreadyknown scientific and technological areas

We consider this book a partial contribution to such a task We have picked up several examplesthat 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 helpfuland useful to the readers

Kvetoslav R Spurny

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Prof Dr Kvetoslav R Spurny was Head of the Department of Aerosol Chemistry at the FraunhoferInstitute for Environmental Chemistry and Ecotoxicology in Germany from 1972 to 1988 Afterhis retirement, he continued to work as an aerosol chemist Prior to this, he was an environmentalchemist at the Institute for Occupational Hygiene in Prague (1952 to 1956) and Head of theDepartment of Aerosol Sciences at the Czechoslovak Academy of Sciences in Prague (1957 to1972) 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 auxRoses, 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 ChemicalSciences at the Czechoslovak Academy of Sciences in Prague in 1964

Professor Spurny was a member of the American Chemical Society, American Association forthe Advancement of Science, American Association of Aerosol Research, British OccupationalHygiene Society, the New York Academy of Sciences, and was president of the Association forAerosol Research from 1983 to 1984 He wrote three books on aerosols and over 150 originalpublications in aerosol physics and chemistry In 1989, he was the recipient of the American DavidSinclair Award in Aerosol Sciences

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Municipal Institute of the State Public

Health Officer Service

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

Heinrich Hühnerfuss

Institute of Organic ChemistryUniversity of HamburgHamburg, Germany

Mark Z Jacobson

Department of Civil and Environmental Engineering

Stanford UniversityStanford, California

G Krier

Laboratoire de Spectrométrie de Masse et Chimie Laser

IPEMMetz, France

Markku Kulmala

Department of PhysicsUniversity of HelsinkiHelsinki, Finland

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

National Heritage Board

Satens Historska Museer

Clouds and Precipitation Group

Istituto delle Scienze dell´Atmosfera e

Cristina Sabbioni

CNRInstituto delle Scienze dell’Atmosfera e dell’Oceano

Euripides G Stephanou

Department of ChemistryEnvironmental Chemical Processes LaboratoryUniversity of Crete

Heraklion, Crete, Greece

Ignatius N Tang

Department of Applied ScienceBrookhaven National LaboratoryUpton, New York

Timo Vesala

Department of PhysicsUniversity of HelsinkiHelsinki, Finland

Giuseppe Zappia

CNRScienze dei Materiali e della Terra Universitá di Ancona

Ancona, Italy

´ Eva Zemplén-Papp

Hungarian Academy of SciencesBudapest, Hungary

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Aerosol Chemistry

WHAT IS AEROSOL CHEMISTRY DEALING WITH?

An aerosol is a collection of fine and very fine particles dispersed in the gas phase Whileaerosol physics tries to describe the mechanical and dynamical behavior of this system and themovement of particles in several force fields, and considers the single particle to be chemicallyinert, aerosol chemistry involves the physicochemical and chemical properties of the particles, inthe 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 severalenvironmental fields and situations Single aerosol particles are rarely inert; they are chemicallyvaried and reactive

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Editor’s Introduction

The physics and chemistry of aerosols have become generally adopted and are commonly in usetoday They fall under aerosol science In general, aerosols, as dispersed systems, have the samehistorical beginning and development as colloid chemistry Both colloid chemistry and aerocolloids(aerosols) originated approximately in the same time period, in the second half of the 19th century.Thomas Graham, who was the first to distinguish between crystalloids and colloids in the 1860s,

is considered the founder of “classical” colloid chemistry The first observations and identifications

of finely dispersed particles in gases, especially in air, were also made during this time period andrecorded by the most important scientists such as J Tyndall (1870), M Coulier (1875), J Aitken(1880), and L.J Bodaszewsky (1881) et al

Princeton, NJ, 1969) A Schmauss, a German meteorologist, was the first to introduce this terminto the literature (Schmauss, A., Kolloidchemie und meterologie, Meteorol Zschr., 37, 1–8, 1920)

He had compared the properties and behavior of colloidal systems in liquids with dispersed systems

in gases As an analogy to the term “hydrosol,” he used the designation “aerosol” for the loids In the publication mentioned, he concluded that: “Between the aerocolloidal solutions andthe systems of solid and liquid particles in the atmosphere, large analogies do exist and thereforethe latter can be named aerosols, while the first ones are known as hydrosols.”

aerocol-Physical investigations of aerosols were the domain of the classical period of aerosol science.Greater practical interest in the properties of and processes in aerosol chemistry began during the1950s “Photochemical smog” was a new term at that time, and started to be used for the designation

of highly dispersed aerosols in the atmosphere of cities, which were heavily polluted by volatileorganics and gaseous and particulate emissions produced primarily by motor vehicles This aerosol

is formed by several photochemical mechanisms and chain reactions in the air after intensive UVirradiation The first important observations and measurements date back to the 1950s (e.g., seeHaagen-Smit, A.J et al.)

The importance of physicochemical processes — such as gas-to-particle conversion (or viceversa), heterogeneous chemical reactions, etc — was recognized Important laboratory and atmo-spheric investigations, including the development of mathematical models, have been undertakensince the 1970s Several laboratories and institutes have taken part in such research In my opinion,the most basic results were published at that time by S.K Friedlander and his “school of aerosolphysics and chemistry” established initially at Cal Tech (California Institute of Technology) inPasadena and continued later at UCLA (University of California at Los Angeles) (See alsoFriedlander,S.K., Smoke, Dust and Haze, John Wiley & Sons, New York, 1971) Friedlander, hispupils, and coworkers were very successful in describing homogeneous and heterogeneous reactionsunder laboratory and atmospheric conditions John Seinfeld, Friedlander’s successor at Cal Tech,and his staff are continuing with aerosol formation studies by developing, describing, and verifyingmathematical models (See also Seinfeld, J.H., Atmospheric Chemistry and Physics of Air Pollution,John Wiley & Son, New York, 1985.)

Another important event dealing with the development of aerosol chemistry was the Conference

Atmo-spheric Chemistry, Geophysical Monograph 26, Am Geophys., Union, Washington, D.C., 1982).The published presentations of this conference showed that heterogeneous or multiphase chemicalprocesses play an important role in general atmospheric chemistry

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The role of chemistry in the polluted atmosphere, as well as in several effects which atmosphericanthropogenic aerosols produce in the total environment (e.g., deterioration of human health,ecosystems, materials, etc.), is perhaps of greatest importance Nevertheless, aerosol chemistry issignificantly involved in several technological fields as well.

A very important one is the technology of the production of new materials by means of aerosolchemical reactions and processes Virtually any material in the form of fine particles with controlledcompositions, microstructures, morphologies, and particle size (ranging from nanometer to micronsize) can be produced by means of this technology (Kodas, T., Ed., Aerosols in material processing,

J Aerosol Sci., 24, 271, 1993.)

A further field in which aerosol chemistry is involved is the technology of combustion processes.Heterogeneous and particle surface chemical reactions are a very important part of the formationand modification processes by aerosol production in burning gases, liquids, and powders (Kaup-pinen, E.I., Ed., Combustion aerosols, J Aerosol Sci., 29, 387, 1998)

It is clear that there exists no sharp dividing line between aerosol physics and aerosol chemistry.Generally speaking, both are involved in the dynamics of any aerodispersed system and in itseffects As mentioned, the literature dealing with aerosol chemistry is still rather widely dispersed,and monographs summarizing and evaluating chemical studies in aerosols seem to be very desirable

Kvetoslav R Spurny

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Physical Chemistry of Aerosol Formation 23

Markku Kulmala, Timo Vesala, and Ari Laaksonen

Chapter 3

The Estimation of Time-Dependent (Relaxation) Processes Related to Condensation and

Evaporation of Liquid Drops 47

Chemical Characterization of Aerosol Particles by Laser Raman Spectroscopy 177

K Hang Fung and Ignatius N Tang

Recent Developments in the Structural Investigation of Aerosols by Synchrotron Radiation:

Application to Ceramic Processing 257

Claude Landron

Chapter 13

Fundamentals and Performance of the MCVD Aerosol Process 271

Vlastimil Matˇejec, Ivan Kaˇsík, and Miroslav Chomát

Calcium in the Urban Atmosphere 347

Marco Del Monte and P Rossi

Chapter 18

Corrosion of Asbestos-Cement Building Materials by the Action of Atmospheric Acidic

Aerosols and Precipitations 365

Chemical Characteristics and Temporal Variation of Size-Fractionated Urban Aerosols

and Trace Gases in Budapest 415

Imre Salma, Willy Maenhaut, Éva Zemplén-Papp, and János Bobvos

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Urban and Rural Organic Fine Aerosols: Components Source Reconciliation Using an

Organic Geochemical Approach 457

Alexandra Gogou and Euripides G Stephanou

Chapter 24

Elimination of Diesel Soots Using Oxidation Catalysts 487

Vincent Perrichon and P Mériaudeau

Transport and Chemistry of Pesticides in the Atmosphere 577

Kai Bester and Heinrich Hühnerfuss

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Part I

General Aspects

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Environmental Effects

K vetoslav R Spurny

CONTENTS

Introduction 3

Secondary Atmospheric Anthropogenic Aerosols 4

Formation, Transformation, and Characterization 4

Particle Size-Dependent Chemistry and Toxicology 4

Increasing Fine Particulate Emissions 9

Health Effects 10

Air Particulate Epidemiology 10

Toxicology of Fine Particulates 10

Clouds, Global Climatic Effects, and Ozone 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 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 black, uranium dioxide, titanium dioxide powders,1 ceramic super-conductors,2 magnetic semiconductors,3 etc

Another field of application of good aerosols is their usage in the field of medicine (i.e., for the production and application of diagnostic and therapeutic aerosols).5

Although the distinction between good and bad aerosols is sharp, there do exist aerosols, for

application in the protection of plants, forest, crops, etc has a very positive impact on agricultural development On the other hand, agroaerosols can also produce negative effects on the health of farms, on atmospheric and aqueous environments, on soils, etc

Generally speaking, some of the good aerosols can also be harmful The nano-sized particles and powders produced in aerosol synthesis can be toxic when inhaled by humans Unfortunately, the majority of anthropogenic aerosols in the ambient air have negative impacts; for example, on human health, on the living as well as nonliving environment, and on several atmospheric processes (climate changes, ozone depletion, cloud formation, and other atmospheric processes) This short

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