Chemical Processes in Atmospheric Oxidation

Georges Le Bras (Orléans) Editor and Coordinator

Oxidation and removal of atmospheric constituents involve complex sequences of reactions which can lead to the production of photo-oxidants such as ozone. In order to understand and model these complex reaction sequences, it is necessary to have a comprehensive understanding of reaction mechanisms and accurate estimates of kinetic parameters for relevant gas-phase atmospheric reactions. This book presents recent advances in the field and includes the following topics: the oxidation of simple organic compounds, NOx kinetics and mechanisms, OH radical production and rate constants for the OH attack on more complex organic compounds, peroxy and alkoxy radical reactions, photo-oxidation of aromatic and biogenic compounds, the interaction between radical species, the nitrate radical and its role in night-time reactions as well as the sources and sinks of HOx and RO₂ radicals. The book is volume 3 of the series on Transport and Chemical Transformation of Pollutants in the Troposphere.

Foreword by the General Editors
Preface by the LACTOZ Steering Group

Chapter 1.

1.1. Summary
1.2. Application of LACTOZ results
1.3. Original objectives and LACTOZ achievements

Chapter 2. Review of the Activities and Achievements of the EUROTRAC Subproject LACTOZ
G. Le Bras

2.1. Reactions of OH radicals
2.2. Reactions of NO₃ Radicals
2.3. Reactions of O₃ with Alkenes
2.4. Reactions of Peroxy Radicals
2.5. Reactions of Oxy Radicals
2.6. Oxidation of Aromatic Compounds
2.7. Oxidation of Aromatic Compounds
2.8. Oxidation of Biogenic Compounds

Chapter 3. Individual Reports from LACTOZ Contributors

3.1. Laboratory Studies of the Atmospheric Decay of Hydrocarbons in the NOx Free Atmosphere
K. Bächmann, B. Kusserow, J. Polzer, J. Hauptmann and M. Hartmann

3.2. OH Initiated Oxidation of VOC Under Variable NOx Conditions
K-H Becker, I. Barnes, A. Bierbach, K.J. Brockmann, F. Kirchner, B. Klotz, H.G. Libuda, A. Mayer-Figge, S. Mönningghoff, L. Ruppert, W. Thomas, E. Wiesen, K. Wirtz and F. Zabel

3.3 . Laboratory and Field Measurement Studies of the Tropospheric Chemistry of Nitrate and Peroxy Radicals
J.P. Burrows, T. Behmann, J.N. Crowley, D.Maric, A. Lastätter-Weißenmayer, G.K. Moortgat, D. Perner and M. Weißenmayer

3.4 . Tropospheric Degradation of Aromatics: Laboratory Kinetic Studies of some First Steps of the OH Initiated Oxidation
P. Devolder, J.P. Sawerysyn, C. Fittschen, A. Goumri, L. Elmaimouni, B. Bigand and C. Bourbon

3.5. Laboratory Studies of the Formation of Hydroperoxides in Ozonolysis of Anthropogenic and Biogenic Alkenes
S. Wolff, W.V. Turner, S. Gäb, S. Mönninghoff, L. Ruppert and K. Brockmann

3.6 . Gas-Phase Reactions of Interest in Night-Time Tropospheric Chemistry
J. Hjorth, N.R. Jensen, H. Skov, F. Cappellani and G. Restelli

3.7 . Laboratory Studies of Peroxy Radical Reactions of Importance for Tropospheric Chemistry
M.E. Jenkin, G.D. Hayman, R. A. Cox and T.P. Murrells

3.8 . The Rates and Mechanisms of the Photo-oxidation Reactions of VOC under Simulated Tropospheric Conditions
J.A. Kerr, D.W. Stocker, M. Semadeni, J. Eberhard and C. Müller

3.9. Laboratory Studies of NO₃ and OH Reactions of Tropospheric Relevance
G. Le Bras, G. Poulet, N. Butkovskaya, V. Daële, D. Johnstone, I.T. Lançar, G. Laverdet, A. Mellouki, A. Ray, S. Téton and I. Vassali

3.10. Peroxy Radical Reactions of Tropospheric Interest
R. Lesclaux, A.A. Boyd, I. Bridier, F. Caralp, V. Catoire, F.F. Fenter, P.D. Lightfoot, B. Nozière, D.M. Rowley, B. Veyret and E. Villenave

3.11. Laboratory Studies of Some Thermal Reactions Involving NOy Species
E. Ljungström, M. Hallqvist, R. Karlsson, S. Langer and I. Wängberg

3.12. High-Resolution Measurements of the Absorption Cross-Sections for O₃ and NO₂
J. Brion, A. Chakir, B. Coquart, D. Daumont, A. Jenouvrier, J. Malicet and M.F. Merienne

3.13. Laboratory Studies of Peroxy Radicals, Carbonyl Compounds and Ozonolysis Reactions of Tropospheric Importance
G.K. Moortgat, D. Bauer, J.P. Burrows, J. Crowley, F. Helleis, O. Horie, S. Koch, S. Limbach, P. Neeb, W. Raber, F. Sauer, C. Schäfer, W. Schneider, F. Simon and C. Zahn

3.14. Atmospheric Chemistry of Nitrogen-Containing Species
O.J. Nielsen

3.15. Kinetic Studies of Reactions of Alkylperoxy and Haloalkylperoxy Radicals with NO. A Structure-Activity Relationship for Reactions of OH with Alkenes and Polyalkenes
J. Peeters, J. Vertommen, I. Langhans, W. Boullart, J. Van Hoeymissen and V. Pultau

3.16. Mechanism and Kinetics of the Reaction of OH with Volatile Organic Compounds
M.J. Pilling, A.E. Heard, S.M. Saunders and P.I. Smurthwaite

3.17. Reactions of n- and s-Butoxy Radicals in Oxygen. Importance of Isomerisation and Formation of Pollutants
K. Sahetchian and A. Heiss

3.18. Gas-phase Ozonolysis of Alkenes and the Role of the Criegee Intermediate
W. Sander, M. Träubel and P. Komnick

3.19. Mechanistic and Kinetic Studies of Selected Oxidation Steps of Tropospheric Interest
R.N. Schindler

3.20. Reactions of OH Radicals with Organic-Nitrogen Containing Compounds
H. Sidebottom, J. Treacy and O.J. Nielsen

3.21. Kinetics and Mechanism for the Reaction of Ozone with Cycloalkenes
H. Sidebottom and J. Treacy

3.22. Mechanisms for the Oxidation of C5-C7 Hydrocarbons
P. Warneck, H.J. Benkelberg and R. Seuwen

3.23. Studies of the Kinetics and Mechanisms of Interactions of Nitrate and Peroxy Radicals of Tropospheric Interest
R.P. Wayne, P. Biggs and C.E. Canosa-Mas

3.24. Time-Resolved Studies of the NO₂ and OH Formation in the Integrated Oxidation Chain of Hydrocarbons
R. Zellner, A. Hoffmann, W. Malms and V. Mörs

3.25. Adduct Formation of OH with Aromatics and Unsaturated Hydrocarbons and Consecutive Reactions with O₂ and NOx to Regenerate OH
C. Zetzsch, R. Koch, B. Bohn, R. Knispel, M. Siese and F. Witte

Chapter 4. LACTOZ Publications 1988-1995