Despite tremendous technological and financial effort in Japan to deal with the effects of the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident many challenges remain. The Government of Japan's Committee on Countermeasures for Contaminated Water Treatment considered existing and proposed measures and technologies "to remove" contaminated water, "to keep out" the inflow of water into the sources of contamination and to "prevent leakage" of contaminated water into the environment. They concluded in a December 2013 report that it was difficult to take effective measures using only existing general knowledge and the committee asked for technical information to be further gathered from both domestic and overseas experts in the following six topics: (1) Storage of contaminated water, (2) Treatment of contaminated water, (3) Removal of radioactive materials from the seawater in the harbour, (4) Control of contaminated water within buildings, (5) Site management to restrict groundwater flowing into the site, and (6) Understanding groundwater flow including the behaviour of radionuclides. In this work efforts will be made to tackle aspects of topics 3, 4 and 5. The most problematic radionuclides at the FDNPP are Sr-90, Cs-134 & Cs-137 because they form highly soluble salts and have environmental behaviour similar to the common (excess) groundwater ions Ca2+ and K+, respectively, hence they are mobile, bioavailable and of immediate concern. Initial work at the FDNPP focused on removal of Cs at the plant and in storage vessels, this project aims to also cover the clean-up of Sr-90 and Co-60. This joint UK/Japan (University of Birmingham, Japanese Atomic Energy Agency, Kyushu University, College of Engineering at Shibaura Institute of Technology) proposal will build on the work of an established internationally leading collaboration for the development, characterisation and testing of three novel systems for immobilisation of radionuclides. The novelty of the first set of materials is that they are designed to be removable by magnetic separation rather than traditional gravity fed fixed bed column system where effluent needs to be pumped into the system. This gives engineering flexibility and scope for use in the field; for example they could be positioned deposited in contaminated water and then magnetically collected along with attached radionuclides. The novelty of the second set of materials are that they are being designed to be made by halophilic organisms, i.e. those that live in high salt concentration environments such as seawater, and could therefore be produced and used in decontamination of harbour seawater or saline groundwater near the FDNPP. The novelty and importance of the final set of materials is a design so that they can be poured or injected into the ground to form porous barriers that will trap the targeted radionuclides and prevent their further migration. All three sets of materials will be characterised using advanced instrumentation so that the mechanism of radionuclide entrapment and the stability of incorporation is fully understood. These materials will not only assist in the clean-up at the FDNPP but will also be available for the abatement of any future accidents and may have a role to play in UK decommissioning activities and legacy waste clean-up. Within this project the goal is to evaluate the scope of the three sets of materials to provide key data and a platform to underpin further development and process implementation in conjunction with Japanese Chemical and Civil Engineers.

Perceived problems of nuclear waste treatment limit the acceptability of nuclear power even though this is the only current alternative to fossil fuels. Green energies still require 10-20 years of development and even then will not completely suffice. Current nuclear waste treatment is OK but the best methods are expensive and/or not very selective. A worrying problem is the black market of stolen 'nuclear' materials for terrorist activities, with pollution of water supplies as one threat This will become less likely if fast, portable clean-up technology is known to be available. The same technology could be used to improve nuclear waste treatment. Currently ion exchange methods suffice but the best are too expensive. Finely-divided material is best but is difficult to fabricate into flow-through columns. We need now materials, better than the commercial ones, combining finely divided yet column-compatible formats, and cheaper. .A new type of ion exchanger was developed which utilises a microbial enzyme to synthesise hydrogen uranyl phosphate (H UP). This is excellent for removal of the radionuclides 137Cs, 9OSr and 60Co. Tests against nuclear wastes in S. Korea showed high effectiveness, radiostabilly & economy compared to commercial products. The trick is that the bacteria template the HUP as a supported high-surface finely divided layer (nanolayer) onto their surfaces and control crystal growth to make, effectively, an ion-exchange bionanolayer (overcoat). Before doing all this, the bacteria first stick themselves (via sticky 'arms' :adhesions) onto a spongy support, don their overcoats and then die but leave behind the (radiostable) active enzyme for more HUP overcoat synthesis. The problem is that uranium is radioactive. This does not matter for wastes which are already radioactive, but would not be popular for public use. Fortunately, the related phosphates of the non-toxic Zr and Ti are also ion exchangers. These are laid down as poorly-crystalline solids (actually this is a better way to obtain metal selectivity) but these have never been considered as BIONANOLAYERS for ion exchange before. The 1st OBJECTIVE is to develop a nano-layered bioinorganic ion exchanger based on bio-Zr,Ti phosphates (overcoats) & determine the selectivity of the coated sponges for the radioisotopes. For use the filtration sponge is packed into a flow-through column but the columns can get partially blocked, losing effectiveness. The 2nd OBJECTIVE is to develop a bioreactor with low channelling and blockage effects using magnetic resonance imaging as a tool to follow metal accumulation processes and flows noninvasively within the reactor Itself, in order to minimise the blockages and achieve maximal efficiency/capacity at lowest cost. The use of predictive mathematical models developed from the MRI data, will help us cut comers In our quest for portable, effective filters. The 3rd OBJECTIVE is to produce the material cheaply (we may need a lot of it, fast), helped by a previous cost analysis (EU report,1995) which showed that the manufacturing costs are comparable to commercial methods. We will undercut these costs by using a natural plant product as our feed material to make the ion exchanging overcoat and by growing the bacteria beforehand on sugary industrial wastes. The methods were demonstrated in previous projects, and proof of principle was shown using the HUP material to treat real nuclear waste. But not so much is known about the Zr/TiP-based ion exchangers and almost nothing about the postbiosynthesis chemical processing needed to produce the best ion exchange material from the starting bionanolayer. We will utilise state of the art biofilm technology, solid state chemistry and MRI to produce and evaluate a completely new material which is robust, which cannot be made chemically and which will fill the huge gaps between what is available and what we need. We will make a movie of the process for the biggest impact

Abstracts are not currently available in GtR for all funded research. This is normally because the abstract was not required at the time of proposal submission, but may be because it included sensitive information such as personal details.

The development of nuclear weapons and energy programmes since the 1940s have created a legacy of nuclear waste and contamination worldwide. In 2012, Sellafield Limited (named as the most hazardous nuclear site in the UK) hit the national press/media when a report by the National Audit Office highlighted the considerable challenges and spiralling costs faced by the UKs Nuclear Decommissioning Authority in taking forward the cleanup of this site. In 2012, the Fukushima Daiichi power plant and surrounding contaminated area (650 km2) also recently hit international news headlines when Tokyo Electric Power Company confirmed the accidental release of 300 tonnes of highly radioactive and concentrated waste water into the Pacific Ocean. An ice wall costing £300m has been pledged to prevent groundwater flow through the most contaminated reactor site but there are still plumes of contaminated groundwater that need to be treated and the decontamination of soil (estimated at 60 Mt) will produce even more complex liquid waste. British Nuclear Fuels invested in 30 years supply of naturally occurring zeolites (clinoptilolite) to remove aqueous Cs+ and Sr2+ from fuel cooling ponds. However, legacy and accidental waste is more complex (e.g. saline wastewater, complex and high organic soil decontamination solutions from Fukushima; and lower radionuclides concentrations and high background competing ions in Sellafield groundwater). Zeolites are inefficient under these conditions (e.g. lower sorption capacity and/or low mechanical strength), therefore, new innovative technologies are required for the safe remediation (cleanup) and entrapment (lockup) of radionuclides from these complex contaminated waters. Under complex chemical conditions, microbially-generated, rapidly produced biominerals have high metal adsorption capacity/functionality compared to natural zeolites and commercially available/laboratory grade materials, arising from their unique morphology and nanoscale properties. For example, biogenic hydroxyapatite materials (HA mass more than ten times the mass of the bacteria that produced it) have durable radionuclide adsorption capacity (up to 30 %wt for radionuclides tested: Actinides (U, Am), Sr and Co under simulated groundwater conditions, against high concentrations of competing ions (0.1-2000 mmol/L Na+, Cl-, Ca2+, Mg2+) and at wide ranging pH conditions (3-9.5); the specific nanostructured morphology of Bio-HA was shown to underlie these advantages. Bio-HA also has proven superior stability against metal remobilisation, economics, & function as compared to commercially available materials and, being biogenic will never run out or require procurement or import from other countries (enabling stable-supply and rapid-response). Additionally we have produced a new Bio-CeP material that shows great promise for Cs remediation. However, both biominerals have not been tested or applied as a permeable reactive barrier or ion exchange technology using environmental conditions found at contaminated sites. The grant will be held at the University of Birmingham, which has an established track record in nuclear research dating back to 1950s, (specifically, nowadays, in remediation, decommissioning, health monitoring and residual life prediction for existing nuclear power stations) and recently led a Policy Commission into the future of nuclear energy in the UK. The grant will also be supported by the National Nuclear Laboratory and the Japanese Atomic Energy Authority enabling the achievement of technology readiness level four, rapid worldwide dissemination of research outcomes and increased societal impact.

30 years' research on metal biorecovery from wastes has paid scant attention to strong CONTEMPORARY demands for (i) conservation of dwindling vital resources (e.g platinum group metals (PGM), recently rare earth elements, (REE), base metals (BMs) and uranium) and (ii) the unequivocal need to extract/refine them in a non-polluting, low-energy way. 21stC technologies increasingly rely on nanomaterials which have novel properties not seen in bulk materials. Bacteria can fabricate nanoparticles (NPs), bottom up, atom by atom, with exquisite fine control offered by enzymatic synthesis and bio-scaffolding that chemistry cannot emulate. Bio-nanoparticles have proven applications in green chemistry, low carbon energy, environmental protection and potentially in photonic applications. Bacteria can be grown cheaply at scale for facile production. We have shown that bacteria can make nanomaterials from secondary wastes, yielding, in some cases, a metallic mixture which can show better activity than 'pure' nanoparticles. Such fabrication of structured bimetallics can be hard to achieve chemically. For some metals like rare earths and uranium (which often co-occur in wastes) their biorecovery from scraps e.g. magnets (rare earths) and wastes (mixed U/rare earths), when separated, can make 'enriched' solids for delivery into further commercial refining to make new magnets (rare earths) or nuclear fuel (U). Biofabricating these solids is often beyond the ability of living cells but they can form scaffolds, with enzymatic processes harnessed to make biomineral precursors, often selectively. B3 will invoke tiered levels of complexity, maturity and risk. (i) Base metal mining wastes (e.g. Cu, Ni) will be biorefined into concentrated sludges for chemical reprocessing or alternatively to make base metal-bionanoproducts. (ii) Precious metal wastes will be converted into bionanomaterials for catalysis, environmental and energy applications. (iii) Rare earth metal wastes will be biomineralised for enriched feed into further refining or into new catalysts. (iv) Uranium-waste will be biorefined into mineral precursors for commercial nuclear fuels. In all, the environment will be spared dual impacts of both primary source pollution AND the high energy demand of processing from primary 'crude'. Metallic scraps are tougher, requiring acids for dissolution. Approaches will include the use of acidophilic bacteria, use of alkalinizing enzymes or using bacteria to first make a chemical catalyst (benignly) which can then convert the target metal of interest from the leachate into new nanomaterials (a hybrid living/nonliving system, already shown). Environmentally-friendly leaching & acids recycle will be evaluated and leaching processes optimised via extant predictive models. The interface between biology, chemistry, mineralogy and physics, exemplified by nanoparticles held in their unique 'biochemical nest', will receive special focus, being where major discoveries will be made; cutting edge technologies will relate structure to function, and validate the contribution of upstream waste doping or 'blending'; these, as well as novel materials processing, will increase bio-nanoparticle efficacy. Secondary wastes to be biorefined will include magnet scraps (rare earths), print cartridges (precious metals), road dusts (PMs, Fe,Ce) & metallurgical wastes (mixed rare earths/base metals/uranium). Their complex, often refractory nature gives a higher 'risk' than mine wastes but in compensation, the volumes are lower, & the scope for 'doping' or 'steering' to fabricate/steer engineered nanomaterials is correspondingly higher. B3 will have an embedded significant (~15%) Life Cycle Analysis iterative assessment of highlighted systems, with end-user trialling (supply chains; validations in conjunction with an industrial platform). B3 welcomes new 'joiners' from a raft of problem holders brought via Partner network backup.