Laboratory studies of Criegee radical reactions
Lead Research Organisation:
University of Bristol
Department Name: Chemistry
Abstract
Chemicals entering the atmosphere come from a number of sources, but in broad terms are either from human activity or from the biosphere (natural systems). What happens to these chemicals once in the atmosphere is very important of course. If they are toxic they can impact on the health of humans, animals and natural ecosystems. Therefore, it is vital that we understand how pollutants are removed by the atmosphere. One very important removal process involves the so called hydroxyl radical. This is an extremely reactive species that acts like a chemical detergent, destroying pollutants and cleaning up the atmosphere. It has emerged in recent investigations that an important source of the hydroxyl radical must be coming from Criegee radicals. However, these Criegee radicals have been impossible to measure until recently. Work carried out by us, using a facility in the USA, has allowed us to observe a Criegee radical for the first time. In this project we will develop a state-of-the-art experimental system that will allow us to investigate the chemistry of Criegee radicals and therefore to help us to understand how they affect the amount of hydroxyl radical is present in the atmosphere. Such work will not only improve our understanding of the urban environment but will also have implications for climate studies as well. Reactions of Criegee intermediates, over a wide range of pressure and temperature, are of importance in atmospheric chemistry. The proposed UV-PE apparatus will be the first of its kind and will enable us to carry out a range of experiments to study reactions of these radicals that, as far as we are aware, no one else in the world can do. To demonstrate how versatile the apparatus is we propose a carefully designed set of experiments to look at the source and fate of Criegee radicals in the troposphere. Quantum chemistry calculations of the reactions studied will provide detailed understanding of their mechanisms and the kinetic data will be incorporated into models describing the troposphere and compared with available measurements.
Organisations
People |
ORCID iD |
Dudley Shallcross (Principal Investigator) |
Publications
Bannan T
(2015)
The first UK measurements of nitryl chloride using a chemical ionization mass spectrometer in central London in the summer of 2012, and an investigation of the role of Cl atom oxidation
in Journal of Geophysical Research: Atmospheres
Boxe C
(2012)
The effect of the novel HO 2 + NO ? HNO 3 reaction channel at South Pole, Antarctica
in Antarctic Science
Caravan RL
(2020)
Direct kinetic measurements and theoretical predictions of an isoprene-derived Criegee intermediate.
in Proceedings of the National Academy of Sciences of the United States of America
Caravan RL
(2018)
The reaction of hydroxyl and methylperoxy radicals is not a major source of atmospheric methanol.
in Nature communications
Chhantyal-Pun R
(2015)
A kinetic study of the CH2OO Criegee intermediate self-reaction, reaction with SO2 and unimolecular reaction using cavity ring-down spectroscopy.
in Physical chemistry chemical physics : PCCP
Chhantyal-Pun R
(2020)
Criegee intermediates: production, detection and reactivity
in International Reviews in Physical Chemistry
Chhantyal-Pun R
(2019)
Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2.
in Physical chemistry chemical physics : PCCP
Chhantyal-Pun R
(2020)
Impact of Criegee Intermediate Reactions with Peroxy Radicals on Tropospheric Organic Aerosol
in ACS Earth and Space Chemistry
Chhantyal-Pun R
(2018)
Criegee Intermediate Reactions with Carboxylic Acids: A Potential Source of Secondary Organic Aerosol in the Atmosphere
in ACS Earth and Space Chemistry
Chhantyal-Pun R
(2017)
Temperature-Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates
in Angewandte Chemie
Chhantyal-Pun R
(2017)
Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH3)2COO.
in The journal of physical chemistry. A
Chhantyal-Pun R
(2019)
Direct Kinetic and Atmospheric Modeling Studies of Criegee Intermediate Reactions with Acetone
in ACS Earth and Space Chemistry
Chhantyal-Pun R
(2017)
Temperature-Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates.
in Angewandte Chemie (International ed. in English)
Copeland G
(2014)
Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.
in Environmental science & technology
Derwent R
(2015)
Tropospheric ozone production regions and the intercontinental origins of surface ozone over Europe
in Atmospheric Environment
Derwent R
(2012)
Seasonal cycles in short-lived hydrocarbons in baseline air masses arriving at Mace Head, Ireland
in Atmospheric Environment
Ghalaieny M
(2012)
Determination of gas-phase ozonolysis rate coefficients of a number of sesquiterpenes at elevated temperatures using the relative rate method.
in Physical chemistry chemical physics : PCCP
Hamer P
(2014)
Investigating the photo-oxidative and heterogeneous chemical production of HCHO in the snowpack at the South Pole, Antarctica
in Environmental Chemistry
Harrison R
(2012)
Atmospheric chemistry and physics in the atmosphere of a developed megacity (London): an overview of the REPARTEE experiment and its conclusions
in Atmospheric Chemistry and Physics
Henne S
(2012)
Future emissions and atmospheric fate of HFC-1234yf from mobile air conditioners in Europe.
in Environmental science & technology
Higgins CM
(2014)
Quantum yields for photochemical production of NO2 from organic nitrates at tropospherically relevant wavelengths.
in The journal of physical chemistry. A
Holland R
(2021)
Investigation of the Production of Trifluoroacetic Acid from Two Halocarbons, HFC-134a and HFO-1234yf and Its Fates Using a Global Three-Dimensional Chemical Transport Model
in ACS Earth and Space Chemistry
Holland R
(2020)
Investigating the Atmospheric Sources and Sinks of Perfluorooctanoic Acid Using a Global Chemistry Transport Model
in Atmosphere
Jones B
(2014)
Airborne measurements of HC(O)OH in the European Arctic: A winter - summer comparison
in Atmospheric Environment
Description | Criegee intermediates react very differently depending on the type of Criegee species and this has important implications for biogenic emissions. We have now investigated the reaction of C1, C2 and C3 Criegee species with carbonyls, alcohols and organic acids and shown that they react rapidly and tend to form addition species which are important in secondary organic aerosol formation. Further work has shown that Criegee Intermediates react with organic hydroperoxides and may be an important source of secondary organic aerosol. |
Exploitation Route | Incorporation into the Leeds University Master Chemical Mechanism, we are also advising governments in South Africa and Thailand in part as a result of this work. |
Sectors | Education,Environment |
Description | In popular articles and on the news, they are also being used in the development of structure activity relationships so that they can be used in modelling studies of the atmosphere. |
First Year Of Impact | 2014 |
Sector | Education,Environment |
Description | Leverhulme Grant Scheme |
Amount | £186,000 (GBP) |
Organisation | The Leverhulme Trust |
Sector | Charity/Non Profit |
Country | United Kingdom |
Start | 02/2014 |
End | 02/2017 |
Description | Please look at http://www.chemlabs.bris.ac.uk/outreach/latest.html this details the myriad outreach work that we do |
Form Of Engagement Activity | A talk or presentation |
Part Of Official Scheme? | No |
Geographic Reach | International |
Primary Audience | Schools |
Results and Impact | We run numerous Outreach activities please refer to the website log. Please read our education papers 1. Criegee Biradicals and Climate Change. D.E. Shallcross and T.G. Harrison. Education in Chemistry 50(5) 22-24, 2013 2. Creating Climate Change Awareness in South African Schools Through Practical Chemistry Demonstrations. Suthananda N Sunassee, Ryan M Young, Joyce D Sewry, Timothy G Harrison, Dudley E Shallcross. Acta Didactica Napocensia 4, 35-48 (2012). 3. Outreach within the Bristol ChemLabS CETL (Centre for Excellence in Teaching and Learning). D.E. Shallcross, T.G. Harrison, T.M. Obey, S.J. Croker, N.C. Norman. Higher Education Studies 3(1), 39-49, 2013 4. |
Year(s) Of Engagement Activity | Pre-2006,2006,2007,2008,2009,2010,2011,2012,2013,2014 |
URL | http://www.chemlabs.bris.ac.uk/outreach/latest.html |