Ruthenium: Nuclear's Volatile Problem

Ruthenium is a fission product possessed of two relatively long lived stable isotopes: Ru-103 (half life = 39.8 days) and Ru-106 (half life = 1 year). Both isotopes are present in UK spent fuel and so have had to be accounted for during the reprocessing or disposal of that fuel. At a number of stages during the processing of spent fuel, ruthenium can be exposed to high nitric acid, high temperature conditions that may lead to its transfer into the gas phase as ruthenium tetroxide. Two such stages are the dissolution of spent fuel into concentrated nitric acid at the start of reprocessing, and the vitrification of ruthenium into a glass waste form after reprocessing has occurred.
Volatilisation is to be avoided as the resultant gas phase ruthenium may then redeposit within metal pipework elsewhere in the plant which will then have to be decontaminated. However, ruthenium volatilisation occurs at unexpectedly low temperatures. Whilst RuO2 is not seen to volatilise below 900oC, gaseous ruthenium oxides have been seen to evolve from solutions of Ru in nitric acid at temperatures as low as 150oC - making the management of ruthenium difficult during reprocessing and vitrification.
Thus, given its volatile nature and high specific radioactivity ruthenium presents a strong challenge to the nuclear industry in effectively managing its abatement. Key challenges are to fully understand the highly complex solution/solid state chemistries that obtain not only under conditions relevant to dissolvers, evaporators and vitrification plants, but also in the decontamination methods used in its clean up. Using a combination of chemical, analytical and engineering approaches, we shall seek to address these challenges in this PhD. The specific objectives of the PhD will be to:
1) Develop gravimetric, mass spectroscopic, electrochemical and spectroscopic analytical methods that will improve the understanding of ruthenium speciation in high nitric acid environments and oxidation state interconversion during oxidative / thermal treatment of same.
2) Using these methods, to establish the kinetics of interconversion between ruthenium species, most especially Ru(III) to Ru(IV) and Ru(VIII) and Ru(IV) to Ru(VIII), and the resultant product distributions of these processes.
3) To establish the influence that Ru(III) complexation may have on these interconversions and the role that RuO2 may have in supporting or inhibiting volatilisation.
4) Establish the mechanism by which other fission product metal ions such as Ce(IV) may oxidise and thus potentially volatilise ruthenium.
5) Investigate the role that key NOx species such as NO and HNO2 may have on oxidising Ru(III) directly or inhibiting the putative Ce(IV)-driven oxidation of Ru(III).

In GREEN we envisage there are potentially Impacts in several domains: the nuclear Sector; the wider Clean Growth Agenda; Government Policy & Strategy; and the Wider Public.

The two major outputs from Green will be Human Capital and Knowledge:

Human Capital: The GREEN CDT will deliver a pipeline of approximately 90 highly skilled entrants to the nuclear sector, with a broad understanding of wider sector challenges (formed through the training element of the programme) and deep subject matter expertise (developed through their research project). As evidenced by our letters of support, our CDT graduates are in high demand by the sector. Indeed, our technical and skills development programme has been co-created with key sector employers, to ensure that it delivers graduates who will meet their future requirements, with the creativity, ambition, and relational skills to think critically & independently and grow as subject matter experts. Our graduates are therefore a primary conduit to delivering impact via outcomes of research projects (generally co-created and co-produced with end users); as intelligent and effective agents of change, through employment in the sector; and strong professional networks.

Knowledge: The research outcomes from GREEN will be disseminated by students as open access peer reviewed publications in appropriate quality titles (with a target of 2 per student, 180 in total) and at respected conferences. Data & codes will be managed & archived for open access in accordance with institutional policies, consistent with UKRI guidelines. We will collaborate with our counterpart CDTs in fission and fusion to deliver a national student conference as a focus for dissemination of research, professional networking, and development of wider peer networks.

There are three major areas where GREEN will provide impact: the nuclear sector; clean growth; Policy and Strategy and Outreach.

the nuclear sector: One of our most significant impacts will be to create the next generation of nuclear research leaders. We will achieve this by carefully matching student experience with user needs.

clean growth - The proposed GREEN CDT, as a provider of highly skilled entrants to the profession, is therefore a critical enabler in supporting delivery of both the Clean Growth agenda, Nuclear Industry Strategy, and Nuclear Sector Deal, as evidenced by the employment rate of our graduates (85% into the sector industry) and the attached letters of support.

Policy and Strategy: The GREEN leadership and supervisory team provide input and expert advice across all UK Governments, and also to the key actors in the nuclear industry (see Track Records, Sections 3.3 & 5.1, CfS). Thus, we are well positioned to inculcate an understanding of the rapidly changing nuclear strategy and policy landscape which will shape their future careers.

Outreach to the wider public: Building on our track record of high quality, and acclaimed activities, delivered in NGN, GREEN will deliver an active programme of public engagement which we will coordinate with activities of other nuclear CDTs. Our training programme provides skills based training in public and media communication, enabling our students to act as effective and authoritative communicators and ambassadors. Examples of such activities delivered during NGN include: The Big Bang Fair, Birmingham 2014 - 2017; British Science Week, 2013 - 2017; ScienceX, Manchester; 2016 - 2018; and The Infinity Festival, Cumbria, 2017.