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
Taatjes CA
(2012)
Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone.
in Physical chemistry chemical physics : PCCP
Boxe C
(2012)
The effect of the novel HO 2 + NO ? HNO 3 reaction channel at South Pole, Antarctica
in Antarctic Science
Lee EP
(2012)
Spectroscopy of the simplest Criegee intermediate CH2OO: simulation of the first bands in its electronic and photoelectron spectra.
in Chemistry (Weinheim an der Bergstrasse, Germany)
Muller J
(2012)
Energy and ozone fluxes over sea ice
in Atmospheric Environment
Le Breton M
(2012)
Airborne observations of formic acid using a chemical ionization mass spectrometer
in Atmospheric Measurement Techniques
Welz O
(2012)
Direct Kinetic Measurements of Criegee Intermediate (CH 2 OO) Formed by Reaction of CH 2 I with O 2
in Science
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
Leather K
(2012)
Acid-yield measurements of the gas-phase ozonolysis of ethene as a function of humidity using Chemical Ionisation Mass Spectrometry (CIMS)
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
Leather KE
(2012)
Temperature and pressure dependence of the rate coefficient for the reaction between ClO and CH3O2 in the gas-phase.
in Physical chemistry chemical physics : PCCP
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
Derwent R
(2012)
Seasonal cycles in short-lived hydrocarbons in baseline air masses arriving at Mace Head, Ireland
in Atmospheric Environment
Le Breton M
(2013)
Airborne hydrogen cyanide measurements using a chemical ionisation mass spectrometer for the plume identification of biomass burning forest fires
in Atmospheric Chemistry and Physics
Percival CJ
(2013)
Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation.
in Faraday discussions
Taatjes CA
(2013)
Direct measurements of conformer-dependent reactivity of the Criegee intermediate CH3CHOO.
in Science (New York, N.Y.)
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
Khan M
(2014)
Reassessing the photochemical production of methanol from peroxy radical self and cross reactions using the STOCHEM-CRI global chemistry and transport model
in Atmospheric Environment
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
Taatjes CA
(2014)
Atmospheric chemistry: intermediates just want to react.
in Nature chemistry
Shallcross DE
(2014)
Criegee intermediates in the indoor environment: new insights.
in Indoor air
Taatjes CA
(2014)
Research frontiers in the chemistry of Criegee intermediates and tropospheric ozonolysis.
in Physical chemistry chemical physics : PCCP
Jones B
(2014)
Airborne measurements of HC(O)OH in the European Arctic: A winter - summer comparison
in Atmospheric Environment
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)
Le Breton M
(2014)
Simultaneous airborne nitric acid and formic acid measurements using a chemical ionization mass spectrometer around the UK: Analysis of primary and secondary production pathways
in Atmospheric Environment
Hamer P
(2014)
Investigating the photo-oxidative and heterogeneous chemical production of HCHO in the snowpack at the South Pole, Antarctica
in Environmental Chemistry
Higgins CM
(2014)
Quantum yields for photochemical production of NO2 from organic nitrates at tropospherically relevant wavelengths.
in The journal of physical chemistry. A
Sewry J
(2014)
Offering Community Engagement Activities To Increase Chemistry Knowledge and Confidence for Teachers and Students
in Journal of Chemical Education
Shallcross DE
(2015)
Reaction between CH3O2 and BrO radicals: a new source of upper troposphere lower stratosphere hydroxyl radicals.
in The journal of physical chemistry. A
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
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
Khan M
(2015)
Global analysis of peroxy radicals and peroxy radical-water complexation using the STOCHEM-CRI global chemistry and transport model
in Atmospheric Environment
Khan M
(2015)
Global modeling of the C1-C3 alkyl nitrates using STOCHEM-CRI
in Atmospheric Environment
Khan M
(2015)
A study of global atmospheric budget and distribution of acetone using global atmospheric model STOCHEM-CRI
in Atmospheric Environment
Khan M
(2015)
The global budgets of organic hydroperoxides for present and pre-industrial scenarios
in Atmospheric Environment
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
Derwent R
(2015)
Tropospheric ozone production regions and the intercontinental origins of surface ozone over Europe
in Atmospheric Environment
Khan M
(2015)
Global modeling of the nitrate radical (NO3) for present and pre-industrial scenarios
in Atmospheric Research
Khan M
(2015)
Estimation of Daytime NO 3 Radical Levels in the UK Urban Atmosphere Using the Steady State Approximation Method
in Advances in Meteorology
Khan M
(2016)
A modelling study of the atmospheric chemistry of DMS using the global model, STOCHEM-CRI
in Atmospheric 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
Khan M
(2017)
A modeling study of secondary organic aerosol formation from sesquiterpenes using the STOCHEM global chemistry and transport model
in Journal of Geophysical Research: Atmospheres
McGillen M
(2017)
Criegee Intermediate-Alcohol Reactions, A Potential Source of Functionalized Hydroperoxides 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
(2017)
Temperature-Dependence of the Rates of Reaction of Trifluoroacetic Acid with Criegee Intermediates.
in Angewandte Chemie (International ed. in English)
Khan MAH
(2018)
Criegee intermediates and their impacts on the troposphere.
in Environmental science. Processes & impacts
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 |