Criegee intermediates and their impacts on the troposphere
Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have e...
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| Published in | Environmental science--processes & impacts Vol. 2; no. 3; pp. 437 - 453 |
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| Main Authors | , , , , |
| Format | Journal Article |
| Language | English |
| Published |
England
Royal Society of Chemistry
01.03.2018
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| Subjects | |
| Online Access | Get full text |
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| Summary: | Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. The decomposition of CIs can be a significant source of OH to the tropospheric oxidation cycle especially during nighttime and winter months. A variety of model-measurement studies have estimated surface-level stabilized Criegee intermediate (sCI) concentrations on the order of 1 × 10
4
cm
−3
to 1 × 10
5
cm
−3
, which makes a non-negligible contribution to the oxidising capacity in the terrestrial boundary layer. The reactions of sCI with the water monomer and the water dimer have been found to be the most important bimolecular reactions to the tropospheric sCI loss rate, at least for the smallest carbonyl oxides; the products from these reactions (
e.g.
hydroxymethyl hydroperoxide, HMHP) are also of importance to the atmospheric oxidation cycle. The sCI can oxidise SO
2
to form SO
3
, which can go on to form a significant amount of H
2
SO
4
which is a key atmospheric nucleation species and therefore vital to the formation of clouds. The sCI can also react with carboxylic acids, carbonyl compounds, alcohols, peroxy radicals and hydroperoxides, and the products of these reactions are likely to be highly oxygenated species, with low vapour pressures, that can lead to nucleation and SOA formation over terrestrial regions.
Criegee intermediates (CIs), carbonyl oxides formed in ozonolysis of alkenes, play key roles in the troposphere. |
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| Bibliography: | Craig Taatjes manages the Combustion Chemistry Department at Sandia National Laboratories in Livermore, CA, USA. He received his PhD from the University of Colorado under the direction of Prof. Stephen Leone and worked as a postdoctoral associate in the labs of Prof. Steven Stolte and Prof. Aart Kleyn. At Sandia his research has concentrated on fundamental kinetics of key reactions in hydrocarbon oxidation. He has received the Polanyi medal of the Gas Kinetics Group of the Royal Society of Chemistry and is a fellow of the American Physical Society. Dudley Shallcross is Professor of Atmospheric Chemistry at the University of Bristol UK. His research interests include gas-phase kinetic studies of free radicals (such as Criegee intermediates) of relevance to the Earth's atmosphere, global and regional modelling of the lower atmosphere and measurements of stable species in the atmosphere using GC-MS. In particular he is interested in how terrestrial and aquatic biogenic emissions may change as climate and pollution levels change and how this may alter atmospheric composition on regional and global scales. He is also a keen science communicator to a wide range of audiences. Anwar Khan is a Senior Research Associate at the Atmospheric Chemistry Research Group (ACRG), University of Bristol. He completed his Ph.D. from the same university in 2008 under the guidance of Professor Dudley E. Shallcross. He worked as a Marie Curie Post-doctoral Fellow in the Institute for Marine and Atmospheric Research (IMAU), Utrecht University (2012-2013) and as a Visiting Associate Researcher in the Department of Geography, University of California Berkeley (2009-2011). His current research involves the development of the global STOCHEM and regional mesoscale WRF-Chem models for atmospheric composition and climate studies using CRI (Common Representative Intermediate) methodologies. Rebecca Caravan is a postdoctoral researcher at the Combustion Research Facility, Sandia National Laboratories, working in the group of Dr Craig Taatjes. She obtained her PhD in Chemistry from the University of Leeds in 2015 in the field of chemical kinetics working under the supervision of Professors Dwayne Heard and John Plane, after her undergraduate degree in Chemistry at the University of Bristol. Her present research focuses on the fundamental mechanisms and chemical kinetics of reactions pertinent to low temperature oxidation and the troposphere. Carl Percival is a research scientist at the Jet Propulsion Laboratory-NASA. His research studies the sources and fate of pollution in the atmosphere. In particular, on the photochemical oxidation of atmospheric volatile organic compounds (VOCs) which has major implications for urban and regional air quality, acid deposition, and global climate. His research is in three main areas: the first is the development of methods to directly observe fundamental gas phase kinetics of key reactions of atmospheric importance in the laboratory. The second area of work focuses on the development of novel analytical techniques to quantify trace species in the atmosphere and the third area is on the study of the interaction of gases with aerosols. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 23 AC04-94AL85000; NA0003525 SAND-2018-1551J USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division USDOE National Nuclear Security Administration (NNSA) |
| ISSN: | 2050-7887 2050-7895 |
| DOI: | 10.1039/c7em00585g |