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Chemosensors for atmospheric peroxyl radical investigations (CAPRI)

Project Description

Atmospheric chemistry lies at the heart of a wide range of environmental issues of substantial societal and economic impacts. Whether it is a changing climate, a reduction in air quality affecting human health or the degradation of ecosystems due to air pollution, the details of this chemistry determines the severity of impacts. Technical innovations have been a key driver for allowing us to understand of this chemistry. This project will exploit one such recent innovation, namely Chemosensors for free-radical detection.

Many thousands of volatile organic compounds (VOCs) are emitted to the atmosphere from natural and human activities. Free-radicals such as hydroxyl (OH) initiate VOC breakdown leading to the formation of peroxyl radicals (RO2). These radicals are the key intermediates in subsequent oxidation steps, leading to ozone formation, photochemical smog and secondary organic aerosols – significantly impacting upon air quality and climate. This radical chemistry thus controls the oxidation capacity of the atmosphere, yields of the most harmful secondary pollutants and hence the severity of the environmental impacts. Computer models can simulate this complex chemistry and allow us to predict and mitigate air quality problems. It is of critical importance that the detailed chemical mechanisms used in such models accurately and adequately represent the most important processes. However, recent results from laboratory, field and theoretical studies demonstrate that RO2 chemistry is poorly understood, for even the most important species. Improved lab experiments are urgently needed, but radical detection has posed considerable challenges to analytical chemistry. Low concentrations, high reactivity, and short lifetimes mean radicals cannot easily be sampled.

This project builds upon previous work to develop novel radical “chemosensors” that efficiently and selectively react with gas-phase RO2, producing non-radical products that conserve the structure of the original radical and allow off-line analysis by mass spectrometry. We will incorporate these chemosensors into a fast-flow reactor for studies of RO2 in a range of atmospheric reactions. We will target important atmospheric RO2, including chlorinated RO2, for which virtually nothing is known. Science outcomes of this project will be key to answering big atmospheric questions such as “how is atmospheric oxidation power maintained?”, “are intramolecular reactions important?”, “what is the role of chlorine in radical recycling chemistry?”, and “what level of detail do atmospheric model mechanisms actually need?”
You will work closely with an interdisciplinary team of leading atmospheric, gas-kinetic and free-radical scientists in York. Expert supervision will ensure appropriate support and guidance. As the project progresses you will:
1) Couple chemosensors to the fast-flow apparatus for characterisation experiments on simple chemical systems and use mass-spectrometry to detect, identify and quantify new target RO2.
2) Use the fast-flow apparatus to determine rate constants and product yields for target RO2 reactions, and explore reaction mechanism pathways, e.g. via isotopic labelling experiments.
3) use chemical box models incorporating the Master Chemical Mechanism (MCM: to design and optimise experiments for the target atmospheric RO2• species.
Previous work resulted in multiple high-impact publications, presentations to international conferences and stimulated new collaborative research worldwide. We therefore envisage a range of high impact publications stimulating interest from across the atmospheric science community.

You will be based in the Wolfson Atmospheric Chemistry Laboratories a unique facility bringing together experts in atmospheric measurements, Earth system models and laboratory chemistry to form the largest integrated UK atmospheric research team. You will develop transferrable skills in design and preforming fast flow gas-phase kinetic experiments, spectrometric characterisation techniques (e.g., Chemical Ionisation Mass-Spec (CIMS), HPLC with mass spectrometry), chemical mechanism development and evaluation, numerical / data skills and kinetic model analysis. Training will be provided in all areas. The successful candidate will have a strong scientific background (good degree in chemistry, physics, engineering or similar), a keen interest in environmental issues, and an aptitude and enthusiasm for experimental work. We appreciate that this project is highly interdisciplinary and encompasses several different science and technology areas. However the York team is well supported with experienced scientists and technical support. No previous experience with specific techniques or instruments is necessary.

More details of the project can be found on the NERC PANORAMA DTP web page (

You will be based in the Department of Chemistry at the University of York.

This PhD project is available to study full-time or part-time (50%).
This PhD will formally start on 1 October 2020. Induction activities will start on 28 September.

Funding Notes

Value: The studentships are fully funded by NERC for 3.5 years and cover: (i) a tax-free annual stipend at the standard Research Council rate (£15,009 for 2019-2020, to be confirmed for 2020-2021 but typically increases annually in line with inflation), (ii) research costs, and (iii) tuition fees at the UK/EU rate.
Eligibility: Unless stated otherwise, fully funded studentships (stipend + fees) are offered to both UK and EU applicants.


Candidate selection process:
• Applicants should submit a PhD application to the university of Leeds by Monday 6 January 2020
• Supervisors may contact candidates either by email, telephone, web-chat or in person
• Supervisors rank the candidates for the assessment panel
• The assessment panel will shortlist candidates for interview from all those nominated
• Shortlisted candidates will be invited to a panel interview at the University of Leeds on the week commencing 24 February 2020
• The Leeds PANORAMA DTP awarding committee will award studentships following the panel interviews
• Candidates will be notified of the outcome of the panel’s decision by email
• Successful candidates will then need to submit a formal PhD application to the University of York

How good is research at University of York in Chemistry?

FTE Category A staff submitted: 47.06

Research output data provided by the Research Excellence Framework (REF)

Click here to see the results for all UK universities

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