Making, Stabilising and Understanding Unusual Intermediate Oxidation States in the Early Actinides

Lead Research Organisation: University of Manchester
Department Name: Chemistry

Abstract

Energy use, especially in the form of electricity is an essential requirement for modern life, and one that most of us could not even contemplate living without. From transport and travel to computers and televisions, the global demand for energy is on the increase. The drawback of recent technological advances however, is that greenhouse gases, in particular CO2 are emitted during the production of energy. Growing public awareness of climate change and its future impacts on the world as we know it have recently shifted the focus from fossil fuel usage to alternative energy sources, and legislation is now in place for reducing the carbon footprint. Among the alternative options, nuclear energy remains the most viable in the short term since the technology is already in place for proficient energy production. Nuclear electricity generation currently supplies around 17 % of the worldwide energy demand (18.4 % in the U.K.) and has already created a legacy of environmental problems due to high level radioactive wastes associated with waste storage and production. This proposal concentrates on the chemistry of the radioactive actinide ions (uranium, plutonium and neptunium) used in the nuclear fuel industry, ways to identify and 'clean up' toxic wastes from the environment and methods to eliminate the need for storing high level wastes in the future. Since the actinides used in current reactors are generated under conditions that are dissimilar to the natural environment, the chemistry of these metals outside of the reactor is completely different and they often exist in unusual oxidation states for a certain period of time before being further altered or reacting. In order to reduce the detrimental impact these radiotoxic wastes have on the environment, it is imperative that we understand their chemistry in full. This can only be achieved by studying the chemistry of these metals in their reactive unstable oxidation states in controlled laboratory conditions using specially designed chemistry. By doing this, we can identify methods of stabilizing these oxidation states and ways for selectively removing them from contaminated sites so that they can ultimately be recycled and used for further energy production. This project will initially examine the chemistry of uranium in the +V oxidation state by synthesizing a range of complexes stabilized by different organic groups under anaerobic conditions, and study the way the chemical groups around them inhibit or enhance reactivity. This chemistry will then be applied to the stabilization of the more radiotoxic elements plutonium and neptunium. At the core of the project is the development of a spectroscopic fingerprint (using time resolved luminescence spectroscopy) of unstable (and stable) oxidation states of these elements in order to develop a non-invasive method of identifying such species in the environment that may exist on a timescale that is too fast using current radiometric and chemical methods.

Publications

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Blackburn OA (2012) Luminescence and upconversion from thulium(III) species in solution. in Physical chemistry chemical physics : PCCP

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Harvey P (2014) Ratiometric detection of enzyme turnover and flavin reduction using rare-earth upconverting phosphors. in Dalton transactions (Cambridge, England : 2003)

 
Description We have successfully established the fluorescence profile of a number of uranium and neptunium compounds in model environmental conditions and aim to use this to image the location and movement of radioactive wastes arising from nuclear fission activities in contaminated lands and geological disposal scenarios.
Exploitation Route Assessment of the chemical and migratory behaviour of actinide ions produced as a result of nuclear fission in biogeochemical environments that will add to the safety case of the world-wide geological disposal of nuclear wastes.
Sectors Energy

Environment

 
Description 'Elucidating Structure and Speciation of Paramagnetic Actinide Complexes by NMR Spectroscopy
Amount £2,500 (GBP)
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 02/2011 
End 03/2012
 
Description Development of a simplified soft donor technique for trivalent lanthanide actinide separations
Amount £991,020 (GBP)
Organisation Batelle Energy Alliance 
Sector Charity/Non Profit
Country United States
Start 11/2010 
End 11/2013
 
Description Development of a simplified soft donor technique for trivalent lanthanide actinide separations
Amount £991,020 (GBP)
Organisation Batelle Energy Alliance 
Sector Charity/Non Profit
Country United States
Start 11/2010 
End 10/2013
 
Description Elucidating Structure and Speciation of Paramagnetic Actinide Asymmetric DOTA Derivatives
Amount £2,500 (GBP)
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 08/2012 
End 10/2012
 
Description Elucidating Structure and Speciation of Paramagnetic Actinide Complexes of Asymmetric DOTA and DTPA Derivatives
Amount £2,500 (GBP)
Organisation European Commission 
Sector Public
Country European Union (EU)
Start 02/2012 
End 03/2013
 
Description Environmental Radioactivity Research Network, Env-Rad-Net
Amount £300,000 (GBP)
Organisation Science and Technologies Facilities Council (STFC) 
Sector Public
Country United Kingdom
Start 01/2012 
End 12/2015
 
Description Equipment for Characterisation and Analysis of Highly Radioactive Materials
Amount £1,256,210 (GBP)
Funding ID EP/I034106/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start  
 
Description IMAGAN: Imaging Protocols to Identify Actinide Speciation and Migration in the Environment
Amount £976,980 (GBP)
Organisation The Leverhulme Trust 
Sector Charity/Non Profit
Country United Kingdom
Start 09/2013 
End 09/2018
 
Description New Directions for EPSRC Research Leaders
Amount £31,150 (GBP)
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 03/2012 
End 04/2014
 
Description Optical Imaging of Uranium Biotransformations by Microorganisms
Amount £620,000 (GBP)
Funding ID NE/R011230/1 
Organisation Natural Environment Research Council 
Sector Public
Country United Kingdom
Start 04/2018 
End 04/2021
 
Description Three Dimensional Optical Imaging of Neptunium Redox Speciation-A Feasibility Study
Amount £196,000 (GBP)
Funding ID EP/R001499/1 
Organisation Engineering and Physical Sciences Research Council (EPSRC) 
Sector Public
Country United Kingdom
Start 06/2017 
End 12/2018
 
Description Actinide NMR 
Organisation Karlsruhe Institute of Technology
Country Germany 
Sector Academic/University 
PI Contribution At the beginning of the Fellowship, we established a collaboration with KIT-INE in Germany, through the FP7-EURACT NMR programme studying the NMR and luminescence spectral properties of actinide complexes of uranium, neptunium, americium and curium. Several families of ligands were synthesised in Manchester and their uranium complexes studied. The ligands were taken to KIT-INE for studies with neptunium, americium and curium.
Collaborator Contribution KIT-INE provided us with time and help accessing the labs, preparing and measuring the samples, including preparation of isotope stocks and negative pressure gloveboxes and trained us on the spectrometers. After the FP7-EURACT programme had finished in 2013, we have continued this collaboration.
Impact Outputs so far include one publication (Chemical Communications 2015), training of PhD students Sean Woodall and Daniel Whittaker who are as a result of this collaboration now employed full time by the National Nuclear Laboratory, UK, instigation of two 2 day international workshops on actinide coordination chemistry for PhD and PDRA researchers, 2014, Manchester, UK and 2015, Karlsruhe, Germany, two successful applications for FP7 EURATOM funded TALISMAN network grant, and 5 invited/plenary research talks for the PI at international f-element conferences. Multidisciplinary-synthetic chemistry, spectroscopy, analytical chemistry
Start Year 2010
 
Description Theoretical Actinide Chemistry 
Organisation Lancaster University
Department Department of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution Visits to UCL and Lancaster University to establish projects of mutual interest.
Collaborator Contribution Our collaborators are experts in computational modelling of the spectroscopic properties of actinide compounds and have modeled the compounds my group has synthesised in the laboratory.
Impact Two publications (RSC Advances and Chemical Communications). Multidisciplinary-synthetic chemistry, spectroscopy and computation
Start Year 2011
 
Description Theoretical Actinide Chemistry 
Organisation University College London
Department Department of Chemistry
Country United Kingdom 
Sector Academic/University 
PI Contribution Visits to UCL and Lancaster University to establish projects of mutual interest.
Collaborator Contribution Our collaborators are experts in computational modelling of the spectroscopic properties of actinide compounds and have modeled the compounds my group has synthesised in the laboratory.
Impact Two publications (RSC Advances and Chemical Communications). Multidisciplinary-synthetic chemistry, spectroscopy and computation
Start Year 2011
 
Description Uranium Emission Spectroscopy 
Organisation Trinity College Dublin
Department School of Chemistry
Country Ireland 
Sector Academic/University 
PI Contribution We collaborated on developing an understanding of the emission spectral properties of uranium (IV) complexes and salts in non aqueous media and hosted a PhD student from Trinity College Dublin for one week where their compounds were remade and measured on our spectrometers.
Collaborator Contribution Our collaborator hosted one of my PhD students for two weeks at Trinity College Dublin to perform some luminescence and cyclic voltammetry measurements on related compounds.
Impact Outputs include, the publication of a joint research paper in RSC Advances, training and cultural exchange for the two PhD students involved and initiation of a long-term collaboration. Multidisciplinary-synthetic chemistry, spectroscopy, analytical chemistry
Start Year 2010
 
Description Bill Newton RSC Award 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact RSC award lecture for Louise Natrajan's 2015 Bill Newton Award. Approximately 40 people attended the event itself, which sparked much discussion and questions afterwards leading to more research groups being aware and interested in our activities
Year(s) Of Engagement Activity 2016
URL http://www.rsc.org/Membership/Networking/InterestGroups/Radiochemistry/BillNewtonAward.asp
 
Description Chemistry in its element podcast 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Chemistry in its element podcast for the magazine Chemistry World. Two 10 minute recorded podcasts with the BBC on the history and uses of the elements 'terbium' and 'ytterbium'
Year(s) Of Engagement Activity 2009
URL http://www.chemistryworld.org/elements
 
Description Departmental Seminars-UK 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Postgraduate students
Results and Impact Invited departmental seminars on our research throughout the UK, on average 2-3 seminars a year.
Year(s) Of Engagement Activity 2009,2010,2011,2012,2013,2014,2015,2016,2017,2018
 
Description Invited conference talks at ACS San Francisco and RERC, Iowa, USA 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited research talks at international conferences in the USA in 2017. Both more general chemistry and specialist chemistry audiences attended.
Year(s) Of Engagement Activity 2017
 
Description Invited plenary lecture at Migration 2016 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact Invited research talk at conference, over 100 people attended and the talk sparked questions and discussions and increased interest in the subject area
Year(s) Of Engagement Activity 2016
 
Description Jodrell Bank Music Festival 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Public/other audiences
Results and Impact Music Festival with live bands and a variety of science stalls with activities and interactive shows.
Year(s) Of Engagement Activity 2012,2013
URL http://www.livefromjodrellbank.com/
 
Description Macclesfield Scibar 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach Local
Primary Audience Public/other audiences
Results and Impact Invited lay talk to the public on my research 'A story of Radioactivity; a Glowing Tale' at Macclesfield Scibar
Year(s) Of Engagement Activity 2017
URL http://macclesfieldscibar.co.uk/
 
Description Manchester Science Spectacular 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Public/other audiences
Results and Impact One day showcase of all research being carried out at The University of Manchester including activities, interactive games.
Year(s) Of Engagement Activity 2010,2011,2012,2013,2014,2015,2017
URL http://www.manchestersciencespectacular.co.uk
 
Description Photoshoot for Dalton Nuclear Institute Brochure 
Form Of Engagement Activity A magazine, newsletter or online publication
Part Of Official Scheme? No
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Photoshoot for advertising the Dalton Nuclear Insitute and its wider activites, I was the representative for Chemistry
Year(s) Of Engagement Activity 2017
 
Description Women of Wonder campaign 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Other audiences
Results and Impact YouTube video, interview and photoshoot with Louise Natrajan for The University of Manchester women of wonder campaign for international women's day 2016.
Year(s) Of Engagement Activity 2016
URL http://www.se.manchester.ac.uk/people/women-of-wonder/
 
Description Women of wonder soft launch 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach Regional
Primary Audience Schools
Results and Impact University of Manchester, women of wonder soft launch event involved each woman of wonder from the STEM Schools (Louise Natrajan, chemistry representative) talking to a selection of female school age students to share stories and inspire them into following a career in science. This inspired many questions and discussion afterwards.
Year(s) Of Engagement Activity 2016
URL https://www.youtube.com/watch?v=R7T-1e-zBto
 
Description YouTube video for School of Chemistry website 
Form Of Engagement Activity A broadcast e.g. TV/radio/film/podcast (other than news/press)
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Media (as a channel to the public)
Results and Impact A short video on our research 'Illuminating Actinides' on the University of Manchester School of Chemistry YouTube Channel, CAMERA
Year(s) Of Engagement Activity 2017
URL https://www.youtube.com/watch?v=ChYkygYqP-Y