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The copper-containing autunite minerals zeunerite [Cu(UO₂)₂(AsO₄)₂•12H₂O], metatorbernite [Cu(UO₂)₂(PO₄)₂•8H₂O] (CuUP), and metazeunerite [Cu(UO₂)₂(AsO₄)₂•8H₂O] (CuUAs) are promising remediation materials for environmental U (and As) contamination. In this thesis, we examine the structure, stability, and synthesis of these mineral phases in order to better understand their long-term stability in the environment. Firstly, we present new structural models for zeunerite, CuUP, and CuUAs to better understand material properties and predict phase behaviour in the environment. In contrast to the existing structural models, which have been exclusively determined via X-ray diffraction, we have conducted structural studies using a combination of neutron powder diffraction (NPD) and ab initio random structure searching (AIRSS). This combined approach is the first of its kind and has allowed us to accurately locate H₂O molecules within the crystal structure and describe a detailed network of hydrogen bonds that contribute towards overall phase stability. Our findings have been published in the International Union of Crystallographers Journal (IUCrJ) and show exciting potential for locating H₂O (and other light elements) in other (trans)uranium materials. In addition to the room temperature structures, we also present new structural models for the high temperature phases that occurred during the dehydration of CuUP and CuUAs (up to 450°C), with applications for predicting the long-term stability of Cu-autunites in hot/ arid climates. We present three high temperature structural models for each material, which were refined from variable temperature NPD data. Our models for CuUP agree with the only previous study but contain more favourable atomic sites. No previous structural models for the high temperature CuUAs phases exist, and we therefore present the first. We also show, for the first time, that high-temperature phase changes for CuUP are reversible, but that the high-temperature phase changes for CuUAs are not reversible under the same conditions. The high temperature treatment did not cause the release of U, P, As, or Cu, and thus heating alone would not likely cause the re-release of remediated U into the environment; instead, the potential re-release of U will hinge on whether the high temperature phases are more or less stable than CuUP and CuUAs under environmental conditions. We then describe the stability of CuUP, CuUAs, and the intermediate composition Cu(UO₂)₂(PO₄)(AsO₄)•8H₂O (CuUPAs) following immersion in bicarbonate solutions (KHCO₃, NH₄HCO₃, and NaHCO₃; 0.5 M) as a function of time. In all cases, the bicarbonate solutions (KHCO₃, NH₄HCO₃, and NaHCO₃) promoted mineral dissolution, with the most extreme effects observed from NaHCO₃. We build on these findings to suggest a U recovery method, with the aim of using recycled U for the fabrication of nuclear fuel. Finally, we describe a novel mechanochemical method for the solid-state synthesis of CuUP and CuUAs, with applications for the remediation of solid waste streams. The mechanochemical method eliminates the need for a solvent in line with the United Nations’ 10 principles of green chemistry, and significantly reduces the risks and costs involved in producing a hazardous liquid waste by-products. We have proven the effectiveness of this technique using both laboratory reagents (proof-of-concept) and a real-world As waste sample received from a smelter plant based in Namibia. Ultimately, we aim for the results presented in this thesis to be used towards stability assessments to determine where autunite remediation materials can be safely used/ stored, without risking the re-release of U (and As) back into the environment.

Additional file 1: Appendix 1. Model Informed Consent Form. Appendix 2. Model Participant Information Sheet.

Additional file 2. SPIRIT Checklist for Trials.

Purpose Workforce development is crucial to the offender personality disorder (OPD) service to provide contemporary, evidenced care and treatment. This study aims to provide an overview and the research evaluation results of a regional higher education programme delivered to a range of criminal justice workers used on the OPD pathway. Design/methodology/approach Three modules were developed and delivered; these are (1) enhancing understanding (20 students), (2) formulation and therapeutic intervention (20 students) and (3) relationships, teams and environments (17 students). A mixed-methods study evaluated participant confidence and compassion. Pre, post and six-month follow-up questionnaires were completed. Additionally, a series of focus groups were conducted to gain in-depth qualitative feedback with a cross-section of students across the modules (N = 7). Quantitative data was collected and analysed separately due to the three modules all having different content. Qualitative data was analysed, and a synthesis of qualitative findings was reported from data taken across the three modules. Findings A total of 52 students participated, drawn from three modules: Module 1 (N = 19); Module 2 (N = 18); Module 3 (N = 15). Confidence in working with people with a personality disorder or associated difficulties improved significantly following completion of any of the modules, whereas compassion did not. Results have been synthesised and have assisted in the future shaping of modules to meet the learning needs of students. Research limitations/implications Further evaluation of the effectiveness of educational programmes requires attention, as does the longer-term durability of effect. Further research is required to explore the post-training impact upon practice, and further exploration is required and larger sample sizes to draw definitive conclusions related to compassion. Practical implications This unique model of co-production that draws upon the expertise of people with lived experience, occupational frontline and academics is achievable and well received by students and can be reproduced elsewhere. Social implications The positive uptake and results of this study indicate a need for expansion of accessible OPD workforce training opportunities across the UK. Further research is required to explore student feedback and comparisons of effectiveness comparing different modes of training delivery, especially in light of the pandemic, which has forced organisations and higher education institutions to develop more digital and distance learning approaches to their portfolios. Originality/value This novel research provides an evaluation of the only higher education credit-bearing modules in the UK focussed solely upon the OPD workforce and aligned with the national drive for non-credit bearing awareness level training “knowledge and understanding framework” (KUF).

IntroductionA growing evidence base demonstrates the effectiveness of supported self-management in stroke for stroke survivors and their families. However, there is significant variation in its implementation in community stroke care and little understanding about how supported self-management works and is delivered across different settings, models used and contexts of community stroke rehabilitation.Methods and analysisUsing a mixed method, realist approach across two phases, this protocol describes a study on community-based supported self-management. The aim is to identify the mechanisms and outcomes of supported self-management in stroke and to understand how supported self-management is implemented in different contexts of community stroke rehabilitation. Phase 1 involves (1) a realist synthesis, (2) a scoping and mapping of current community rehabilitation settings and (3) a Q-methodology study to develop initial programme theories about how community-based supported self-management works, for whom and in what contexts. Phase 2 involves realist informed interviews/focus groups with stroke survivors, community rehabilitation practitioners and team managers from across Scotland to test and refine programme theories and an explanatory model for how supported self-management works across different contexts of community-based stroke rehabilitation.Ethics and disseminationEthical approval and R&D approvals have been granted from East of Scotland Research Ethics Committee (REC reference number: 19/ES/0055) and participating NHS boards. An understanding of how, for whom and in what contexts community-based supported self-management works will help to strengthen its delivery in practice. Such an understanding will enable the design of context-specific recommendations for policy and practice that genuinely reflect the challenges in implementing supported self-management in community stroke care. Results will be disseminated to clinical partners working in community stroke rehabilitation, stroke survivors and families and to policymakers and third sector partners involved in the provision of long-term support for people affected by stroke.PROSPERO registration numberCRD42020166208.

Additional file 1: Additional material 1. Topic guide.

Additional file 2: Additional material 2. COREQ checklist.

Additional file 1:. SPIRIT 2013 Checklist

Additional file 2:. The TIDieR (Template for Intervention Description and Replication) Checklist