Every day, large quantities of volatile organic compounds (VOCs) are emitted into the atmosphere from both anthropogenic and natural sources. The formation of gaseous and particulate secondary products caused by oxidation of VOCs is one of the largest unknowns in the quantitative prediction of the earth’s climate on a regional and global scale, and on the understanding of local air quality. To be able to model and control their impact, it is essential to understand the sources of VOCs, their distribution in the atmosphere and the chemical transformations which remove these compounds from the atmosphere.
In recent years techniques for the analysis of organic compounds in the atmosphere have been developed to increase the spectrum of detectable compounds and their detection limits. New methods have been introduced to increase the time resolution of those measurements and to resolve more complex mixtures of organic compounds. Volatile Organic Compounds in the Atmosphere describes the current state of knowledge of the chemistry of VOCs as well as the methods and techniques to analyse gaseous and particulate organic compounds in the atmosphere. The aim is to provide an authoritative review to address the needs of both graduate students and active researchers in the field of atmospheric chemistry research.
Table of Contents:
Preface ix
List of Contributors xi
1 Volatile Organic Compounds in the Atmosphere: An Overview 1
Jonathan Williams and Ralf Koppmann
1.1 Introduction 1
1.2 Sources 3
1.3 Sinks 5
1.4 Atmospheric distribution 7
1.5 Measurement tools 9
1.6 Modelling tools 10
1.7 How organic species affect the atmosphere 12
1.8 Open questions and future directions 15
References 19
2 Anthropogenic VOCs 33
Stefan Reimann and Alastair C. Lewis
2.1 Introduction 33
2.2 Sources of anthropogenic VOCs 33
2.3 Atmospheric distribution of VOCs 45
2.4 Chemical behaviour of VOCs in the atmosphere 55
2.5 Measurement techniques 60
References 70
3 Biogenic VOCs 82
Allison H. Steiner and Allen L. Goldstein
3.1 Introduction 82
3.2 Sources of biogenic VOCs 83
3.3 Emission inventories of biogenic VOCs 97
3.4 Global distribution of biogenic VOCs 103
3.5 Impact on photooxidants and atmospheric chemistry 107
3.6 Sampling and measurement techniques 114
3.7 Future directions 116
References 117
4 Oxygenated Volatile Organic Compounds 129
Ralf Koppmann and Jürgen Wildt
4.1 Introduction 129
4.2 Tropospheric mixing ratios and global distribution 130
4.3 Sources of OVOCs 137
4.4 Sinks of OVOCs 149
4.5 Budgets and emission inventories 154
4.6 Sampling and measurement techniques 155
4.7 Future directions 160
Acknowledgement 160
References 160
5 Halogenated Volatile Organic Compounds 173
Simon J. O’Doherty and Lucy J. Carpenter
5.1 Introduction 173
5.2 Sources of halogenated VOCs 179
5.3 Atmospheric concentrations: trends and distribution 187
5.4 Sinks of halogenated VOCs 192
5.5 Emission inventories 204
5.6 Sampling techniques 207
5.7 Measurement techniques 210
References 214
6 PAN and Related Compounds 221
James M. Roberts
6.1 The chemistry of PANs 222
6.2 Atmospheric formation 229
6.3 Measurement and calibration techniques 237
6.4 Atmospheric measurements 243
6.5 Modelling and interpretation of ambient measurements 249
6.6 Conclusions 255
Acknowledgements 256
References 256
7 Organic Nitrates 269
Paul B. Shepson
7.1 Introduction 269
7.2 Production mechanism 271
7.3 Measurement methods 274
7.4 Atmospheric measurements 276
7.5 Fate 282
7.6 Conclusions 285
References 286
8 High-Molecular-Weight Carbonyls and Carboxylic Acids 292
Paolo Ciccioli and Michela Mannozzi
8.1 Introduction 292
8.2 Sources 293
8.3 Atmospheric levels 309
8.4 Reactivity and impact on the atmosphere 324
8.5 Sampling and analysis 329
8.6 Conclusions 333
References 334
9 Organic Aerosols 342
Thorsten Hoffmann and Jörg Warnke
9.1 Introduction 342
9.2 Carbonaceous aerosols 345
9.3 Analysis of organic aerosols 365
Further reading 375
References 375
10 Gas Chromatography-Isotope RatioMass Spectrometry 388
Jochen Rudolph
10.1 Introduction 388
10.2 Fundamentals of stable isotope ratios of VOCs 389
10.3 Experimental methods 405
10.4 Kinetic isotope effects 420
10.5 Stable isotope ratios of atmospheric VOC and their sources 447
10.6 Conclusions 458
References 460
11 Comprehensive Two-Dimensional Gas Chromatography 467
Jacqueline F. Hamilton and Alastair C. Lewis
11.1 Introduction 467
11.2 Fundamentals of comprehensive gas chromatography 468
11.3 Modulators 471
11.4 Detectors 474
11.5 Examples of GC × GC use in atmospheric samples 475
11.6 Conclusions 482
Further reading 486
References 486
Index 489
Color plate appears between pages 268 and 269
About the Author :
Ralf Koppmann was until recently deputy director of the Institute for Chemistry and Dynamics of the Geosphere, Institute II: Troposphere at the Research Centre Jülich, Germany and is now Professor of Physics and head of the Atmospheric Physics Department at the University of Wuppertal, Germany. Contributors:
Dr Lucy J. Carpenter
Dr Paolo Ciccioli
Prof. Allen Goldstein
Dr. Jacqui F. Hamilton
Professor. Thorsten Hoffmann
Dr Alastair C. Lewis
Dr Michela Mannozzi
Dr Simon O’Doherty
Dr. Stefan Reimann
Dr James Roberts
Dr. Jochen Rudolph
Dr Paul Shepson
Dr. Allison Steiner
Dr Joerg Warnke
Dr. Jürgen Wildt
Dr. Jonathan Williams
Review :
"The aim of the book, and well achieved, is to provide an authoritative review to address the needs of both graduate students and active researchers in the field of atmospheric chemistry." (International Journal of Environmental and Analytical Chemistry, July 2008)
