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
Wright M
(2014)
Indoor and outdoor atmospheric ion mobility spectra, diurnal variation, and relationship with meteorological parameters Indoor/outdoor air ion mobility spectra
in Journal of Geophysical Research: Atmospheres
White I
(2014)
A feasibility study of the use of reactive tracers to determine outdoor daytime OH radical concentrations within the urban environment
in Atmospheric Science Letters
Welz O
(2014)
Rate coefficients of C(1) and C(2) Criegee intermediate reactions with formic and acetic Acid near the collision limit: direct kinetics measurements and atmospheric implications.
in Angewandte Chemie (International ed. in English)
Welz O
(2012)
Direct Kinetic Measurements of Criegee Intermediate (CH 2 OO) Formed by Reaction of CH 2 I with O 2
in Science
Wasiuk D
(2015)
An aircraft performance model implementation for the estimation of global and regional commercial aviation fuel burn and emissions
in Transportation Research Part D: Transport and Environment
Wasiuk D
(2016)
A mitigation strategy for commercial aviation impact on NO x -related O 3 change
in Journal of Geophysical Research: Atmospheres
Wasiuk D
(2016)
A Commercial Aircraft Fuel Burn and Emissions Inventory for 2005-2011
in Atmosphere
Wasiuk D
(2016)
The impact of global aviation NOx emissions on tropospheric composition changes from 2005 to 2011
in Atmospheric Research
Vansco MF
(2020)
Experimental Evidence of Dioxole Unimolecular Decay Pathway for Isoprene-Derived Criegee Intermediates.
in The journal of physical chemistry. A
Taatjes CA
(2019)
Reaction of Perfluorooctanoic Acid with Criegee Intermediates and Implications for the Atmospheric Fate of Perfluorocarboxylic Acids.
in Environmental science & technology
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 |