Low-Temperature Chemistry of the Atmosphere

Transcription

1 Low-Temperature Chemistry of the Atmosphere

2 NATO ASI Series Advanced Science Institutes Series A series presenting the results of activities sponsored by the NA TO Science Committee, which aims at the dissemination of advanced scientific and technological knowledge, with a view to strengthening links between scientific communities. The Series is published by an international board of publishers in conjunction with the NATO Scientific Affairs Division A Life Sciences B Physics C Mathematical and Physical Sciences o Behavioural and Social Sciences E Applied Sciences F Computer and Systems Sciences G Ecological Sciences H Cell Biology I Global Environmental Change Plenum Publishing Corporation London and New York Kluwer Academic Publishers Dordrecht, Boston and London Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest NATo-pea DATABASE The electronic index to the NATO ASI Series provides full bibliographical references (with keywords and/or abstracts) to more than contributions from international scientists published in all sections of the NATO ASI Series. Access to the NATO-PCO DATABASE compiled by the NATO Publication Coordination Office is possible in two ways: - via online FILE 128 (NATO-PCO DATABASE) hosted by ESRIN, Via Galileo Galilei, Frascati, Italy. - via CD-ROM "NATO Science & Technology Disk" with user-friendly retrieval software in English, French and German ( WTV GmbH and DATAWARE Technologies Inc. 1992). The CD-ROM can be ordered through any member of the Board of Publishers or through NATO-PCO, Overijse, Belgium. Series I: Global Environmental Change, Vol. 21

3 Low-Temperature Chemistry of the Atmosphere Edited by Geert K. Moortgat Atmospheric Chemistry Department Max-Planck-Institut for Chemie Mainz, Germany Austin J. Barnes Department of Chemistry and Applied Chemistry University of Salford Salford M5 4WT, U.K. Georges Le Bras Laboratoire de Combustion et Systemes Reactifs CNRS F Orleans Cedex 2, France John R. Sodeau School of Chemical Sciences University of East Anglia Norwich NR4 7TJ, U.K. Springer-Verlag Berlin Heidelberg New York London Paris Tokyo Hong Kong Barcelona Budapest Published in cooperation with NATO Scientific Affairs Division

4 Proceedings ofthe NATO Advanced Study Institute on Low-Temperature Chemistry of the Atmosphere, held at Maratea, Italy, August 29 - September 11, 1993 ISBN-13: : / e-isbn-13: CIP data applied for This work is subject to copyright. All rights are reserved. whether the whole or part of the material is concerned. specifically the rights oftranslation. reprinting. reuse of illustrations. recitation. broadcasting. reproduction on microfilm or in any other way. and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September in its current version. and permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution under the German Copyright Law. Springer-Verlag Berlin Heidelberg 1994 Softcover reprint of the hardcover 1 st edition 1994 Typesetting: Camera ready by authors SPIN / Printed on acid-free paper

5 PREFACE This volume is based on the lectures presented at the NATO Advanced Study Institute on "Low Temperature Chemistry of the Atmosphere" that took place at the Hotel Villa del Mare, Acquafredda di Maratea, Italy between the 29th August and 11th September, The purpose of the meeting was to review and assess the currently available knowledge of the homogeneous and heterogeneous chemical and physical processes occurring in the troposphere and stratosphere, especially during the "ozone hole" event. Four principal aspects were covered during the ASI: theoretical (chemical and physical), experimental (laboratory studies), observational (field, Antarctic, Arctic) and modelling. The meeting began with an overview of atmospheric chemistry, followed by reviews of relevant homogeneous reactions occurring in the gas phase and the microphysics and physical chemistry of heterogeneous processes that occur on, or in, aerosols, rain and ice. Low temperature laboratory studies were compared with related fieldwork measurements, particularly in relation to the formation and composition of polar stratospheric clouds (PSCs). Measurements in glacial ice were also discussed because they provide a valuable method for assessing the distribution and concentration trends of trace gas species. Finally the state-ofthe-art in chemical modelling of the troposphere and stratosphere, including heterogeneous processes, was discussed. The editors are grateful to the contributors for the trouble that they h~ve taken to expand their lectures into the authoritative accounts presented in this volume. Our thanks are also due to the 67 participants, from 20 countries, whose active involvement made the meeting an outstanding success. Finally we thank the NATO Scientific Affairs Division for their sponsorship, without which the Advanced Study Institute could not have been held. G. K. Moortgat A. 1. Barnes G. LeBras 1. R. Sodeau

6 CONTENTS Preface G. K Moortgat, A. J. Barnes, G. Le Bras and J. R. Sodeau Atmospheric Chemistry: Introduction R.P. Wayne The Elements of Stratospheric and Tropospheric Chemistry RP. Wayne Clouds, Rain and Aerosols P. Warneck Gas Phase Homogeneous Kinetics D.M Golden Laboratory Kinetics at Low Temperature G. LeBras Atmospheric Photochemistry and Spectroscopy A. Weaver and A. R Ravishankara Nucleation Processes in the Atmosphere P. Mirabel and N. Miloshev Aqueous Solution Chemistry P. Warneck Phase Diagrams P. Mirabel and D. Taleb Surface Chemistry M A. Chesters and A. B. Horn Heterogeneous Chemistry and Kinetics D. M Golden and L. R Williams Laboratory Studies of Heterogeneous Reactions M A. Tolbert Chemistry in Sulfate Aerosols A. R. Ravishankara and D. R Hanson Surface Spectroscopy M A. Chesters and A. B. Horn

7 VIII Spectroscopic Studies ofpscs M A. Tolbert, A. M Middlebrook and B. G. Koehler Matrix Isolation Spectroscopy: Technique and Applications A. J. Barnes Photochemistry in and on Low Temperature Solid Materials J. R Sodeau Cryogenic Sampling Techniques G. K Moortgat and D. W. T. Griffith Ice Core Chemistry: Implications for our Past Atmosphere M Legrand Trends in Global Distribution of Trl',e Gases Inferred from Polar Ice Cores M Legrand, D. Raynaud, J.-M ~arnola and J. Chappel/az Global Tropospheric Chemistry P. J. Crutzen Modelling the Chemistry and Micro-Physics of the Cold Stratosphere Th. Peter and P. J. Crutzen Index