The introduction of the Enhanced Actinide Removal Plant (EARP) at Sellafield in 1994 was designed to decontaminate radioactive effluents produced during nuclear fuel reprocessing. Through the action of flocculation with iron, followed by filtration, the effluents are decontaminated before being discharging to sea. The plant has been in successful operation for the past 20 years, and has made a significant difference to the level of radioactivity of the waste. However, little is known about the formed flocs. Particular concern focuses around future changes to the effluent compositions to be processed through EARP. These future feeds will potentially contain significantly less iron, thus potentially impacting upon the flocculation process and the efficiency of the decontamination process. The effluents currently treated contain significant concentrations of iron, stemming from the Magnox fuel reprocessing plant, along with actinides, fission and corrosion products. The flocculation of these acidic radioactive ferric feeds results in the formation of solid iron hydroxide flocs with encapsulated radioactivity. The flocs are then filtered, encapsulated and stored. It is envisioned that by characterising the floc properties, both physically and chemically a greater understanding of EARP can be obtained, ultimately leading to a maintained process efficiency with alternative feed compositions. The effect of a reduction in iron concentration on the chemical and physical properties of the flocs has been studied. The presence of any iron in the mock effluents was found to beneficially increase the contaminant decontamination factors (DF). However, the efficacy of this increase varied between contaminates. The DFs of group I and II metals ranged from 7.10 to 1.19 while lead ranged from 4x105 to 1.60, dependent upon iron concentration. Transition metal and lanthanide contaminants were marginally affected. With the use of agar embedding, the 'liquid form' of the flocs has been retained for two and three dimensional observations. SEM/EDX analysis has allowed for the inspection and chemical characterisation of the flocs while 2D microscope image analysis has allowed for the study of floc size and shape. A range of diameters, 300 - 1500 micro metre were found. Three dimensional X-ray Computer Tomography (3D X-ray CT) conducted at the Manchester X-ray Imaging Facility (MXIF) has led to the physical characterisation and classification of the flocs. Further, by studying the 3D shape it has been possible to classify a floc as a granule, fibre, chip or blade according to the Zingg classification with the majority of formed flocs being classified as granules.

The UK has a large and growing inventory of higher activity radioactive waste awaiting safe long term disposal. The international consensus is to dispose of this radioactive and toxic waste within a deep geological repository, situated 200-1,000 metres beneath the ground surface. The deep geological disposal facility is designed to be a series of engineered and natural barriers. Groundwater forms an integral component of the natural barrier because it 1) controls the flux of reactive components towards the engineered repository, and 2) forms one of the primary transport mechanism through which released radionuclides can be transported away from the repository. The timescale of protection provided by the natural barrier exceeds those provided by the engineered barriers. Knowledge of the regional hydrogeology is a vital step towards predicting the long term performance of any potential repository site. Topically, a UK government decision in 2017 to re-open a nation-wide repository location search has now created a renewed mandate for site exploration. This research aims to determine the regional groundwater characteristics of three UK settings, selected to be hydrogeologically distinct, in order to determine which, if any, offers natural long term hydrogeological containment potential. The settings selected for analysis include Sellafield in West Cumbria, the Tynwald Basin within the East Irish Sea Basin, and Thetford within East Anglia. Site selection is based on diverse groundwater characteristics, and on previous research suggesting potential hydrogeological suitability at these locations. This research is novel in that it provides, for the first time, a direct comparison between the characteristics and qualities of different regional groundwater settings to contain and isolate radioactive waste, based on UK site specific data. Large and detailed numerical models for the three sites, covering areas of 30 km length by 2- 4 km depth have been developed using the open source finite element code 'OpenGeoSys'. The models couple the physical processes of liquid flow and heat transport, in order to replicate regional scale groundwater flow patterns. Models are calibrated to measured rock properties, and predict groundwater behaviour 10,000 years into the future. Uncertain parameter ranges of lithological and fault permeabilities, and peak repository temperatures are tested to determine the possible range of groundwater outcomes. Geochemical retention is assessed separately and validated using the finite difference modelling software 'GoldSim'. Worst case groundwater characteristics for containment and isolation at each site are compared to an 'ideal' benchmark far-field hydrogeological outflow scenario, and scored accordingly using a newly proposed method of assessment. Results show that the Tynwald Basin offers the best potential of the three sites for natural radionuclide containment, performing between 3.5 and 4 times better than Sellafield, and between 1.7 and 4 times better than Thetford. The Tynwald Basin is characterised by 1) long and deep groundwater pathways, and 2) slow local and regional groundwater movement. Furthermore, the Tynwald Basin is located at a feasible tunnelling distance from the coast, adjacent to the UK's current nuclear stockpile at Sellafield, and thus could provide a simple solution to the current waste legacy problem. Results from the Sellafield model indicate that this location cannot be considered to exhibit beneficial characteristics due to short and predictable groundwater pathways which ascend, from the repository, towards surface aquifers. Finally, Thetford within East Anglia has never been drilled to depth so that sub-surface rock properties of basement, located beneath layered sediments, are based on evidence inferred from around the UK. Uncertainties in rock properties has produced a wide range of groundwater characteristic possibilities, with results indicting prospective performance to range from 0 to 2.4 times better than Sellafield. As such, the hydrogeological suitability to host a potential deep geological repository is promising when modelled with most-likely permeability values, but cannot be accurately determined at present. Consideration of decaying heat from the heat emitting waste packages at the three sites reveal that the natural groundwater flow patterns can be distorted up to as much as 7 km away from the theoretical repository, depending on setting. This thus changes the use of the term 'near-field' for safety assessments, as implying an area within the immediate vicinity of the excavated repository site. The overarching findings from this research are that: 1) some locations have greater long term radionuclide containment and isolation prospectivity than others, due to variable quality far-field geological and hydrogeological characteristics; 2) the effect of radiogenic heat emission on the natural groundwater flow pattern is dependent on the site specific geological and hydrogeological characteristics, and therefore so is the area defined as the 'near-field'; and 3) a simple method of site comparison is possible for regional groundwater system under steadystate conditions. Recommendations are for scoping models of regional groundwater settings to be used as a comparative tool, such as undertaken as part of this research, to differentiate between potential sites at an early stage of the current UK site selection programme.

Since the beginning of the nuclear era, starting during the 1940s, large amount of radioactivity has been released into the environment. This thesis deals with the temporal and spatial distribution of the anthropogenic radioisotope 129I (T1/2= 15.7 Myr) in northern Europe. A routine sample preparation procedure for extraction of iodine from milligram amounts of solid materials has been developed and aimed for measuring the 129I concentration by the ultra-sensitive accelerator mass spectrometry method. The technique was further used for the analysis of 129I in sediments collected from two lakes in Sweden and one lake in Finland as well as sediments from two sites in the Baltic Sea. In addition, 129I concentrations in aerosol samples from northern and southern Sweden covering the period 1983 to 2000 have been measured. The results reveal a gradual increase in the anthropogenic 129I fluxes since the 1950s that are linked to emissions from the nuclear fuel reprocessing facilities in Sellafield (UK) and La Hague (France). A sharp increase coinciding with the Chernobyl accident is identified from the Swedish lakes located in areas characterised by relatively high Chernobyl fallout. Numerical modeling of the 129I deposition predicts that >50% of the flux to the lake sediments is related to the liquid emissions from the reprocessing facilities. The modeling also reasonably simulates the contribution of the Chernobyl event to the total 129I flux. The novel time series from northern Europe on 129I in aerosols show about one order of magnitude higher concentration in northern compared to southern Sweden. Estimate of 129I dry fallout based on the aerosol data suggests <25% contribution to the total fallout. The distribution of 129I in the sediment archives demonstrates the potential of the isotope as a new time marker for chronological and environmental investigations.

Two long-lived halogen radionuclides (36Cl, T1/2 = 301 kyr, and 129I, T1/2 = 15.7 Myr) have been studied by means of Accelerator Mass Spectrometry (AMS) at the Uppsala Tandem Laboratory. The 36Cl measurements in natural samples using a medium-sized tandem accelerator (~1 MeV/amu) have been considered. A gas-filled magnetic spectrometer (GFM) was proposed for the separation of 36Cl from its isobar, 36S. Semi-empirical Monte-Carlo ion optical calculations were conducted to define optimal conditions for separating 36Cl and 36S. A 180° GFM was constructed and installed at the dedicated AMS beam line. 129I has been measured in waters from the Arctic and North Atlantic Oceans. Most of the 129I currently present in the Earth's surface environment can be traced back to liquid and gaseous releases from the nuclear reprocessing facilities at Sellafield (UK) and La Hague (France). The anthropogenic 129I inventory in the central Arctic Ocean was found to increase proportionally to the integrated 129I releases from these reprocessing facilities. The interaction and origin of water masses in the region have been clearly distinguished with the help of 129I labeling. Predictions based on a compartment model calculation showed that the Atlantic Ocean and deep Arctic Ocean are the major sinks for the reprocessed 129I. The variability in 129I concentration measured in seawater along a transect from the Baltic Sea to the North Atlantic suggests strong enrichment in the Skagerrak–Kattegat basin. The 129I inventory in the Baltic and Bothnian Seas is equal to ~0.3% of the total liquid releases from the reprocessing facilities. A lake sediment core sampled in northeastern Ireland was analyzed for 129I to study the history of the Sellafield releases, in particular the nuclear accident of 1957. High 129I concentration was observed corresponding to 1990 and later, while no indication of the accident was found. The results of this thesis research clearly demonstrate the uniqueness and future potential of 129I as a tracer of processes in both marine and continental archives.