The gas phase atmospheric photolysis and reactions of key alkyl nitrates and their role in NOy partitioning.
Lead Research Organisation:
University of Bristol
Department Name: Chemistry
Abstract
Alkyl nitrates play a crucial role in controlling the budgets of secondary organic aerosols, ozone, NOx, NOy and HOx throughout the troposphere and the importance of these families in determining atmospheric composition, the earth's radiative balance and any future change in climate can not be overemphasised. A number of recent regional and global model studies have demonstrated that vital kinetic and photolytic parameters, especially for the alkyl nitrates formed from the oxidation of biogenic volatile organic compounds, are missing, preventing atmospheric chemical models from describing oxidant chemistry well and hence determining lifetimes of key greenhouse gases and surface pollutants. These kinetic and photolytic parameters include their loss rate via photolysis, loss rate via reaction with OH and O3 and whether NOx is released on reaction with OH and O3. In this study a combination of Turbulent-Flow Chemical Ionisation Mass Spectrometry coupled with a Gas chromatography- electron capture detector (GC-ECD) for the detection of alkyl nitrates will be used to characterise the kinetics of reaction with OH of key alkyl nitrates, whilst a relative rate technique coupled with GC-ECD and GC-MS will be used to characterise the kinetics of reaction of unsaturated organic nitrates with O3 and a state of the art flash photolysis cavity ring system will be used to measure the photolysis and quantum yield of organic nitrates. Such data will be incorporated into models describing the troposphere and compared with available measurements. The proposed work will be crucial to the understanding of the effects of biogenic volatile organic compounds on atmospheric pollution and climate change.
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
Chhantyal-Pun R
(2019)
Experimental and computational studies of Criegee intermediate reactions with NH3 and CH3NH2.
in Physical chemistry chemical physics : PCCP
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
Foulds A
(2021)
Abundance of NO3 Derived Organo-Nitrates and Their Importance in the Atmosphere
in Atmosphere
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
Khan M
(2015)
Global modeling of the C1-C3 alkyl nitrates using STOCHEM-CRI
in Atmospheric Environment
Khan M
(2015)
The global budgets of organic hydroperoxides for present and pre-industrial scenarios
in Atmospheric Environment
Khan M
(2015)
Global modeling of the nitrate radical (NO3) for present and pre-industrial scenarios
in Atmospheric Research
Khan M
(2021)
Changes to simulated global atmospheric composition resulting from recent revisions to isoprene oxidation chemistry
in Atmospheric Environment
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
Khan M
(2020)
Investigating the Impacts of Nonacyl Peroxy Nitrates on the Global Composition of the Troposphere Using a 3-D Chemical Transport Model, STOCHEM-CRI
in ACS Earth and Space Chemistry
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)
Estimation of Daytime NO 3 Radical Levels in the UK Urban Atmosphere Using the Steady State Approximation Method
in Advances in Meteorology
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
Khan M
(2020)
Global and regional model simulations of atmospheric ammonia
in Atmospheric Research
Khan M
(2021)
Investigation of Biofuel as a Potential Renewable Energy Source
in Atmosphere
Khan MAH
(2021)
Investigating the background and local contribution of the oxidants in London and Bangkok.
in Faraday discussions
Khan MAH
(2018)
Criegee intermediates and their impacts on the troposphere.
in Environmental science. Processes & impacts
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
Le Breton M
(2012)
Airborne observations of formic acid using a chemical ionization mass spectrometer
in Atmospheric Measurement Techniques
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
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
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
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
Percival CJ
(2013)
Regional and global impacts of Criegee intermediates on atmospheric sulphuric acid concentrations and first steps of aerosol formation.
in Faraday discussions
Sewry J
(2014)
Offering Community Engagement Activities To Increase Chemistry Knowledge and Confidence for Teachers and Students
in Journal of Chemical Education
Silva H
(2015)
Modulation of urban atmospheric electric field measurements with the wind direction in Lisbon (Portugal)
in Journal of Physics: Conference Series
Taatjes CA
(2013)
Direct measurements of conformer-dependent reactivity of the Criegee intermediate CH3CHOO.
in Science (New York, N.Y.)
Taatjes CA
(2012)
Direct measurement of Criegee intermediate (CH2OO) reactions with acetone, acetaldehyde, and hexafluoroacetone.
in Physical chemistry chemical physics : PCCP
Taatjes CA
(2014)
Research frontiers in the chemistry of Criegee intermediates and tropospheric ozonolysis.
in Physical chemistry chemical physics : PCCP
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)
The impact of global aviation NOx emissions on tropospheric composition changes from 2005 to 2011
in Atmospheric Research
Wasiuk D
(2016)
A Commercial Aircraft Fuel Burn and Emissions Inventory for 2005-2011
in Atmosphere
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
Weber J
(2021)
Improvements to the representation of BVOC chemistry-climate interactions in UKCA (v11.5) with the CRI-Strat 2 mechanism: incorporation and evaluation
in Geoscientific Model Development
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
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
Winiberg FAF
(2018)
Reaction kinetics of OH + HNO3 under conditions relevant to the upper troposphere/lower stratosphere.
in Physical chemistry chemical physics : PCCP
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
Description | Organic nitrates in the atmosphere are formed through the reaction of organic free radicals and nitrogen oxides (NOx). It emerges that in natural environments naturally occurring free radicals assist terrestrial plants in particular by sequestering NOx formed by soil bacteria that are released into the atmosphere. Once formed these organic nitrates can be deposited to the surface and provide much needed nitrogen to the plant. However, in polluted environments these organic nitrates can store NOx and release it later on in an air masses history leading to ozone formation. In this study we have been able to characterise a number of organic nitrates and their chemical reactivity so that we can determine whether they are likely to deposit (good) or assist on ozone formation (bad). |
Exploitation Route | We are generating data for updates to the MCM (Master Chemical Mechanism) so that these data can be used more widely |
Sectors | Environment,Transport |
Description | Examples in science teaching in UK secondary schools |
First Year Of Impact | 2014 |
Sector | Education |
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 | Primary Science Teaching Trust (PSTT) |
Organisation | Primary Science Teaching Trust (PSTT) |
Country | United Kingdom |
Sector | Academic/University |
PI Contribution | The PSTT run a U.K. wide network of outstanding primary school teachers and science and we have worked with them to develop our website for the project and to support primary schools to use the U.K. air quality archive, see https://pstt.org.uk/resources/curriculum-materials/citizen-science-air-pollution. |
Collaborator Contribution | PSTT Fellows, primary school teachers who have won the Primary Science Teacher of the Year Award, have worked with us to review material and provide additional supporting material to help teachers and their children to use the resources we have developed. Many schools have used the materials developed, particularly in lockdown and it has been reported that parents have been particularly pro-active in the first lockdown. Schools report that parents who do not normally participate in school activities have been working with their children on these projects. We have published two papers that will not appear in the normal research fish list: Harrison, T.G., A.J. Trew, M.A.H. Khan, R. Holland and D.E. Shallcross (2020b). A new resource designed to allow primary children to investigate atmospheric pollution using Defra's Air Quality archive. J. Emergent Science, 19, 25-31. Can current science research in the biological sciences be used in primary school children's scientific enquiry? Alison J. Trew, Lucy Bird, Craig Early, Rebecca Ellis, Timothy G. Harrison, Julia Nash, Katharine Pemberton, Naomi K.R. Shallcross, Caroline Skerry, Paul Tyler and Dudley E. Shallcross, J. Biol. Ed. in press (2021). |
Impact | We have published two papers that will not appear in the normal research fish list: Harrison, T.G., A.J. Trew, M.A.H. Khan, R. Holland and D.E. Shallcross (2020b). A new resource designed to allow primary children to investigate atmospheric pollution using Defra's Air Quality archive. J. Emergent Science, 19, 25-31. Can current science research in the biological sciences be used in primary school children's scientific enquiry? Alison J. Trew, Lucy Bird, Craig Early, Rebecca Ellis, Timothy G. Harrison, Julia Nash, Katharine Pemberton, Naomi K.R. Shallcross, Caroline Skerry, Paul Tyler and Dudley E. Shallcross, J. Biol. Ed. in press (2021). The collaboration involves, primary and secondary school teachers, their schools, the children and their parents, the PSTT and a range of researchers at the University of Bristol |
Start Year | 2020 |
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 |