Nirex is seeking to develop a deep underground repository for the disposal of solid intermediate-level and low-level radioactive wastes (ILW and LLW) in the UK. One possible influence on the behaviour of radionuclides is the formation of water-soluble complexants by the degradation of the solid organic polymers that will be present in the wastes. The degradation products of cellulose have been shown to increase the solubility of plutonium and other radionuclides and to reduce sorption onto near-field and far-field materials. Degradation of cellulose under anaerobic alkaline conditions produces a range of organic acids. In this paper 2-C-(hydroxymethyl)-3-deoxy-D-pentonic acid (isosaccharinic acid, ISA) is identified by High Performance Liquid Chromatography as a significant component of cellulose leachates. A combination of fractionation of cellulose leachates and plutonium solubility determinations shows that ISA is responsible for the majority of the enhancement of plutonium solubility observed in such leachates. Further degradation of ISA by chemical or microbial action may lessen the effect of degraded cellulose leachates. Experimental studies on the chemical degradation of this compound under alkaline conditions suggest that the presence of oxygen is required. Microbial degradation studies show that the plutonium solubility in solutions of ISA is reduced by their exposure to microbial action.

59Ni may make significant contributions to calculated doses in performance assessment (PA) studies of geological repositories for radioactive waste, due principally to the adoption of relatively high near-field solubilities. Ni concentration values used in PA are typically 1–6 orders of magnitude greater than those measured in natural groundwaters. This difference is a result of the utilisation in PA of solubility data for pure nickeliferous solids, and in some instances, the selection of solids chemically incompatible with the disposal environment. The geochemical behaviour of Ni is reviewed. It is considered highly unlikely that Ni will form discrete pure solids in the repository near-field, so that partition as a trace element into solid solutions should be considered. Henry’s law behaviour of trace elements is discussed and geochemically-realistic Ni solubility values for HLW and L/ILW disposal scenarios calculated. It is concluded that Ni will behave according to the chemical conditions of the disposal environment, which should be reflected in the choice of solubility data for PA. The adoption of solid solution modelling for other elements of interest to PA should be considered.

Concentration profiles in rock matrix around water-carrying fissures were measured at Palmottu U deposit. The profiles were interpreted by the classical matrix diffusion concept. Site-specific sorption studies were performed for U using standard batch experiments and surface complexation modelling; the response of sorption isotherms was also tested. Sitespecific matrix properties as well as initial and boundary conditions were used in simulations. Our results indicate that matrix diffusion alone cannot explain the observed enrichment of U and its daughters in the rock matrix.

Locally oxidising conditions in the near-field of the Cigar Lake uranium deposit was observed. Ongoing processes of water radiolysis has also been predicted previously by our mass transport model. In the ore there was an enhanced concentration of helium, hydrogen and sulphate. Sulphate is the only oxidising species of substantial amount in the groundwater samples, and is possibly indirectly produced by water radiolysis and oxidation of sulphides. The ongoing oxidant production rate has been calculated by the mass transport model.

In this paper, the issue of water radiolysis is addressed from a more fundamental angle of approach. The maximum oxidant production rate is calculated based on the assumptions of geometric dispersion of the ore constituents, the estimate of the total radiation energy, the fraction of energy deposited into the pore water, and the G-values of water. The results show that only a few percent of the total radiation energy is deposited into the pore water to cause water radiolysis. If the recombination factor projected by other researchers are accounted for, the oxidant production rate thus calculated agrees with the present-day ongoing oxidant production rate predicted by the mass transport model.

New mineralogical and isotopic studies were carried out on samples from the Bangombé natural nuclear reactor. This reactor is located at shallow depth in the weathering profile and has been subjected to severe supergene alteration. Textural evidence indicates partial dissolution of uraninite in the Bangombé ore related to precipitation of Fe-Ti oxi-hydroxides and clay minerals (kaolinite and metahalloysite). As a consequence of the alteration of the uraninite, uranium and f issiogenic rare earth elements were released in the clayey border of the reactor, whereas radiogenic 232Th remained confined in the close vicinity of the core. A retention effect is also evidenced, under reducing conditions, in the black shales located above the reactor.

This paper describes the mineralogy of a phyllosilicate/uraninite/galena-bearing vein located within the hydrothermal alteration halo associated with the Bangombé reactor. Phyllosilicates within the vein include a trioctahedral Al-Mg-Fe chlorite (ripidolite), Al-rich clay (kaolinite and/or donbassite) and illite. Textural relations obtained by backscattered-electron imaging suggest that ripidolite crystallized first among the sheet silicates. Uraninite is spatially associated with ripidolite and probably precipitated at a later time. While energy-dispersive x-ray analyses suggest that the uranium phase is predominantly uraninite, coffinite or other phases may also be present.

The ∼2 Ga old Oklo, Okelobondo and Bangombé natural reactors in the Republic of Gabon contain solid graphitic bitumens and clay minerals, both of which have effected the containment, or partial containment, of 235U and several fission products. In laboratory experiments, sorption of 134Cs by illite, and illite coated with petroleum was measured in aqueous NaCl solutions to simulate subsurface (connate) waters in sedimentary rocks. Elevated temperatures and increasing salinity of the NaCl solutions facilitated the removal of sorbed cesium from illite.

This mineralogical study was completed to elucidate the relationships between uranium distribution and alteration products of the host rock of natural reactor zone 2 at Oklo. The samples used were from the reactor core and reactor zone clays just below the reactor core. Uraninite is preserved without any alteration in the reactor core. Uranium minerals found to be present in the fractures in the reactor zone clays associated with iron-mineral veins, galena and Ti-bearing minerals. Uranium, for which the phases could not be identified, occurs in iron-mineral veins and the iron-mineral rim of pyrite grains in the reactor zone clays. Uranium is not associated with granular iron minerals occurring in the illite matrix of the reactor zone clays. The degree of crystallinity and uranium content of the three iron-bearing alteration products suggest that they formed under different conditions; the granular iron minerals, under alteration conditions where uranium was not mobilized while the iron-mineral veins and the iron-mineral rim of pyrite, under conditions in which uranium is mobilized after the formation of the granular iron minerals.

A rock specimen, collected downstream of the Koongarra uranium ore deposit, Australia, was examined mainly by high resolution transmission electron microscopy in order to understand the uranium fixation mechanism. Uranium was found to exist as saleeite (Mg(UO2)2(PO4)2.10H2O) microcrystals of 1 – 20 nm scattered between iron minerals (mainly goethite and hematite) of 2 – 50 nm. The microtextural relationship between saléeite and the iron minerals revealed that the iron minerals function as catalyst for the formation of saléeite. The intermediate metamict microstructures of the saléeite microcrystals are consistent with the estimated formation age of saléeite, 1 to 3 × 106 years. Uranium has been, thus, fixed as saléeite downstream as well as in the secondary ore deposit. Saléeite in the secondary ore deposit showed completely periodic to fully metamict microstructures, suggesting that saléeite, a major uranium mineral in the secondary ore deposit, probably began to form a few million years ago and continued to form for the next million years.

A modelling study has been completed to understand the effect of rock alteration on uranium migration at the Koongarra ore deposit, Australia. The model considers the weathering process, the mechanism and rate of chlorite alteration, a major mineral of the host rock, and assumes the presence of reversible sorption sites of chlorite and the presence of reversible and irreversible sorption sites of the weathering products. One- and two-dimensional, calculated uranium concentrations were compared with those observed. Good agreement between the calculated and observed uranium concentration profiles was obtained only when an appropriate fraction of uranium is fixed to the irreversible sorption sites of Fe-minerals produced during weathering of chlorite. On the other hand, the conventional Kd model failed to estimate an adequate uranium concentration profile. The results suggest that the fixation of uranium to Fe-minerals has dominated the migration of uranium in the vicinity of the Koongarra ore deposit.

Gamma spectrometry without any self-absorption correction was developed to measure low energy gamma rays emitted by uranium and actinium series radionuclides in rock samples and groundwater residues collected at the Koongarra ore deposit, Australia. Thin samples were prepared to minimize the self-absorption by uranium in the samples. The present method gave standard deviations of 0.9 to 18% for the measurements of concentrations of uranium and actinium series radionuclides. The concentrations of 238U, 230Th and 235U measured by gamma spectrometry were compared with those by alpha spectrometry that requires a complicated chemical separation procedure. The results obtained by both methods were in fairly good agreement, and it was found that the gamma spectrometry is applicable to rock and groundwater samples having uranium contents up to 8.1% (103 Bq/g) and 3 Bq/1 of 238U, respectively. The detection limits were calculated to be of the order of 10−2 Bq/g for rock samples and 10−2 Bq/1 for groundwater samples. The concentrations of uranium and actinium series radionuclides can be determined precisely in these samples using gamma spectrometry without any self-absorption correction.

El Berrocal is an abandoned uranium mine in a mineralised quartz vein hosted by a Hercynian granite in central Spain. This mine is the focus of an international project to characterise and model natural elemental migration in a fractured-rock environment as an aid to understanding and predicting processes that may occur in a geological repository for radioactive wastes.

Uranium in the mineralised quartz vein has been shown to have originated from the orthomagmatic uraninite in the granite with the elemental removal and migration occurring predominately by hydrothermal fluids. Mobilisation of uranium from the mineralised quartz vein and from granite adjacent to hydraulically-active fractures away from the vein occurred over the geologically-recent past and in the present-day. The most recent mobilisation is evidenced by dissolution features seen in SEM photomicrographs; mineral growth and sorption signatures identified by enhanced uranium concentrations on the surfaces of preexisting minerals; and measured disequilibrium in the uranium series for whole rock close to fracture walls.

Present-day groundwaters in the studied area are young meteoric waters. They are generally calcium-sulphate enriched, oxidising and mildly acidic near the surface, becoming more bicarbonate-rich with near neutral pH in the deeper zones, except around the mineralised vein where the waters are acid (pH around 3) due to oxidisation of the sulphide minerals. No deep, chemically-reducing groundwaters have yet been identified in the El Berrocal boreholes.

Measurements of chemical compositions of groundwaters, carbon isotope analysis of dissolved inorganic carbon and batch experiments on water-rock interaction have been carried out in order to evaluate the chemical evolution of groundwater in the sedimentary rocks of the Tono area, Japan. The activities of Na and Ca ions in the groundwater plotted along the boundary between Na- and Ca-montmorillonite stability fields on a diagram of 2pH+log[Ca2+] vs. pH+log[Na+], which indicates that the two mineral phases are in equilibrium. Groundwater samples, rich in Ca ions (14.8 ppm Ca ions and 16.3 ppm Na ions), were collected from the shallow zone of the Tono area, and were reacted with the sedimentary rocks in the batch experiments. The experiments have revealed that ion exchange occurs between Na ions in the rock samples and Ca ions in the groundwater samples, and the final solutions became rich in Na ions (1.2 ppm Ca ions and 35.2 ppm Na ions). The results of the batch experiments are in agreement with the variation of Na and Ca concentrations in the groundwater in the sedimentary rocks. The carbon isotope data showed that the fraction of HCO3 derived from the dissolution of calcite increases from 25% to 75% of the total HCO3 content with increasing depth. The molality of Na ions in the groundwater was measured to be twice that of HCO3 ions derived from calcite, which supports the Na and Ca ion exchange in the groundwater. The results suggest that the chemical evolution of the groundwater is characterized by the variation in Na, Ca and HCO3 concentrations, and that ion exchange and dissolution of calcite are dominant reactions in the evolution of groundwater in the Tono area.

Hydrothermal veins, rich in Ti, Zr, rare earth elements (REE’s), and actinides, occur in the pure dolomitic marbles of the Adamello contact metamorphic aureole. A selective phase extraction using 9M HC1 was applied to samples from within and near these veins to chemically separate acid-soluble phases from residual phases, and to study the associations of U, Th, and REE’s with these phases. The samples were from the phlogopite, titanian clinohumite, and forsterite vein zones, and from the country rock. The effects of the extraction were studied by SEM/EDS and by chemical analysis. Isotopes of U and Th were analysed by alpha-spectrometry.

The chemical data and SEM/EDS results indicated that dolomite, calcite, apatite, and much of the pyrrhotite were dissolved by the 9M HC1, whereas spinel, phlogopite, titanite, chal copy rite, and zirconolite were among the acid-resistant phases. In all vein samples, the REE-patterns of acid-soluble phases were consistent with the dissolution of REE-rich apatite. In samples from the phlogopite zone, the majority of U, Th, and REE’s were in residual phases, and the REE pattern of the residue was similar to that of REE-rich titanite. In the titanian clinohumite zone, a substantial proportion of these elements were in acid-soluble phases, and the REE pattern of the residual phases resembled that of zirconolite. Clinohumite was partially dissolved by the HC1 treatment. The sample from the forsterite zone contained substantial amounts of REE's in acid-soluble phases, whereas Th and U were mostly in residual phases. The dolomite (country rock) samples contained small amounts of an acid-resistant, uranium-rich phase which, while only comprising about 0.2% of the mass, accounted for 40–60% of the uranium present.

The objective of this study is to develop a conceptual flow-path model for nuclide migration in fractured crystalline rock at the Kamaishi In-Situ Test Site because improvement of existing models of matrix diffusion |e.g. 1,2|, based on realistic geological data, is necessary for a better understanding of nuclide migration into rock matrix. Data from field observations indicate that fractures at the Kamaishi In-Situ Test Site can be classified into three types; type A with a zone of fracture fillings, type B with a zone of fracture fillings and an altered zone, type C consisting of several fractures with a zone of fracture fillings and an altered zone. Fracture type B was studied in detail by laboratory experiments because type B is predominant in the studied area with more than 60 % of a total of 400 fractures observed in the fracture mapping. Data from laboratory experiments on core, crosscutting a water-bearing fracture and the surrounding rock, indicate that the zone of fracture fillings and the altered zone in the vicinity of the fracture contain flow-paths in which nuclides can migrate and be trapped. The fracture fillings contain more interconnected and permeable flow-paths than the altered and unaltered zones. This implies that migrating nuclides can access flow-paths in the altered zone. The altered zone adjacent to the zone of the fracture fillings contains flow-paths such as microfractures, cracks within quartz, and grain boundaries between altered minerals, through which nuclides will migrate from the fracture fillings into the altered zone and be trapped. The fracture fillings and the specimen of the altered zone have higher sorption capacity than the specimen of the unaltered zone. These data suggest that retention of nuclides can be expected in the vicinity of the fracture. In conclusion, a conceptual flow-path model consisting of a zone of fracture fillings, an altered zone, and an unaltered zone has been developed for a better understanding of nuclide migration in fracture type B.

Alteration minerals from a drill-core (maximum depth 2002 m) in the granitic rock at Ashio, central Japan, were studied by optical microscopy, X-ray diffractometry and analytical scanning electron microscopy. In the host rock, biotite is altered to chlorite and plagioclase to illite. Calcite has precipitated in veinlets and grain boundaries. The host rock close to fractures is strongly altered, whereas the rocks distant from fractures are less altered. Quartz, illite, chlorite, laumontite and calcite have precipitated on fracture walls. The alteration minerals are estimated to have formed in the range 140–200°C, higher than the present temperature (13°96°C). The chemical composition of the ground water in the granitic rock at Ashio was estimated thermodynamically from the mineral assemblage. The alteration reaction of palgioclase and the precipitation of calcite may occur simultaneously. The alteration minerals formed in the host rock and in the fractures may adsorb radionuclides effectively, and thus may inhibit radionuclide transport to biosphere.

Examples of the application of natural-analog studies to the estimation of the consequences of a volcanic eruption penetrating a radioactive waste repository are given, including the criteria for analog selection and new data from ongoing studies. Examples of early modeling results focusing on the spatial and temporal scale of subsurface processes are also provided. All of these examples are taken from studies of the potential Yucca Mountain repository, Nevada, but similar approaches could be applied in other areas. In addition, studies of subsurface processes initiated by magmatic events serve as useful analogs for repository thermal loading studies.

The extractive properties of two malonamide extractants, DMDBO3NPDA and DMDBMA were investigated for the extraction of lanthanide(III) and uranyl(VI) ions in benzene-nitric acid systems. It was found that DMDBO3NPDA has a higher extractive capacity than DMDBMA. The difference in their extracting capacities is discussed, based on the enthalpy changes for the extraction reactions and IR data for complexes of metal nitrates with malonamides. In addition, the applicability of a mixed solvent of n-dodecane and some aliphatic alcohols as a diluent for DMDBO3NPDA was examined. The longer the carbon chain and the higher the concentration of the aliphatic alcohol, the more the phase compatibility improves. The distribution ratios of neodymium(III) ion increase with an increase in the carbon chain length of linear aliphatic alcohol and with a decrease in its concentration.

The technique of radiolytic decomposition of water leading to hydrogen production was demonstrated to explore a new field in the utilization of radioactive platinum group metals recovered from high level radioactive waste (HAW) and radioactivity of HAW. The radiation photocatalytic method is based on the technique to decompose water on platinized semiconductor particles under UV-light irradiation which has been widely investigated to develop an alternative energy source. In this study gamma radiation from Co-60 source was applied to produce hydrogen instead of UV-light and a significant amount of hydrogen evolved from catalyst-water suspension. Our preliminary experiments proved a possibility of converting the energy of radiation ionization into chemical energy (hydrogen) by the radiation photocatalytic method.

The extraction behavior of technetium from aqueous hydrofluoric acid solution has been investigated. The recovery of Tc using two techniques, primary amine extraction in mixed heptane and 1–octanol solution and stripping with a mixed aqueous ammonium hydroxide – ammonium carbonate solution has been studied. The determination of distribution ratios and percentages of technetium in both extraction and stripping cycles was established as were the volume ratios between organic and aqueous phases. The stripping mechanism in the aqueous solution has also been investigated by the slope analysis method.