Most countries intend to dispose of their high-level radioactive wastes by converting them into a solidified wasteform which is to be buried within the earth. SYNROC is a titanate ceramic wasteform which has been designed for this purpose on the basis of geochemical principles. It comprises essentially rutile TiO2, ‘hollandite’ Ba(Al,Ti)Ti6O16, zirconolite CaZrTi2O7, and perovskite CaTiO3. The latter three phases have the capacity to accept the great majority of radioactive elements occurring in high-level wastes into their crystal lattice sites. These minerals (or their close relatives) also occur in nature, where they have demonstrated their capacity to survive for many millions of years in a wide range of geological environments. The properties of SYNROC and the crystal chemistry of its constituent minerals are reviewed in some detail and current formulations of SYNROC are summarized. A notable property of SYNROC it its extremely high resistance to leaching by groundwaters, particularly above 100°C. In addition, it can be shown that the capacity of SYNROC minerals to immobilize high-level waste elements is not markedly impaired by high levels of radiation damage. Current investigations are focused on developing a satisfactory production technology for SYNROC and progress towards this objective is described. The high leach resistance of SYNROC at elevated temperatures increases the range of geological environments in which the waste may be finally interred; in particular, SYNROC is well adapted for disposal in deep drill-holes, both in continental and marine environments. The fact that SYNROC is comprised of minerals which have demonstrated long-term geological stability is significant in establishing public confidence in the ability of the nuclear industry to immobilize high-level wastes for the very long periods required.

Radioactive particulate matter (identified as hot particles) is present in the effluent discharged by the British Nuclear Fuels Ltd (BNFL) uranium reprocessing plant at Sellafield, Cumbria, UK. There is very little information on the abundance or chemical and physical forms of solid matter in the effluent; even less is known of the significance of particulate debris in relation to the uptake of radionuclides for non-occupationally exposed people as a result of transfer along marine foodchains. Some observations on the occurrence and abundance of hot particles in the vicinity of Sellafield are reported, with special reference to those that contain transuranic radionuclides (Pu,Am,Cm). Some of the uncertainties are discussed in an evaluation of the significance of hot particles, albeit aggregates of colloids for the smallest particles, and exposure to man from ionizing radiation. There is no evidence that hot particles derived from BNFL and subsequently dispersed into the marine environment represent a hazard to man. However, further studies are required in order to determine whether or not the pathways followed by the particles are significant, or different to those of other radionuclides through which the radiation exposure of man within this region of Cumbria is assessed.

A borosilicate glass, containing 25 wt. % of simulated high-level radioactive waste has been reacted with water at 350°C and 500 bars for 14 and 48 days using large-volume ‘cold-seal’ high-pressure equipment. Under these conditions the glass crystallizes a suite of mineral phases including: albite, NaAlSi3O8; aegirine, NaFeSi2O6; riebeckite, Na2Fe2(Fe,Mg)3Si8O22(OH)2; zektzerite, LiNaZrSi6O15; barium-strontium molybdate, (Ba,Sr)MoO4; stillwellite, (Nd,Ce,La)BSiO5; willemite, Zn2SiO4; smectite; a lithium-sodium borosilicate hydrate; melilite (åkermanite), Ca2MgSi2O7. A description of the morphology of these phases is given, together with a number of chemical analyses. The implications of the incorporation of waste species in these mineral phases to the disposal of high-level radioactive waste is discussed.

The uptake of 137-Cs and 90-Sr on to synthetic zeolite A has been studied. The use of a combined barium exchange followed by a relatively mild heat treatment has been shown to fix the isotopes within a collapsed zeolite structure. Leaching experiments using deionized and simulated sea and pond waters were carried out on zeolite compacts and zeolite/cement composites. They demonstrated the effectiveness of the calcination and cement containment. Some comments on the interpretation of leach test data are made.

Cementitious matrices are being assessed for immobilization of radioactive wastes. This paper discusses some mineralogical aspects of cement chemistry and the uses of siliceous minerals as selective sorbants to enhance immobilization potential.

Studies of sorption and leaching of caesium from pulverized fuel ash (PFA), blast furnace slag, tobermorite, xonotlite, and clinoptilolite are reported. The role of incorporation of these additives in cement and the effect on the nature of the composite matrix on caesium behaviour has been investigated. Specific mechanisms of the interaction of additives with highly alkaline cement environment are described. While slags, PFA, and clinoptilolite undergo reaction at different rates, tobermorite and xonotlite appear to be stable in cement.

Fluid flow through a fractured granite core and leaching experiments on granite powder (at constant temperatures of 50 and 100°C and during cooling from 100 to 50°C) indicate that the dissolved silica content of the fluids originates from the dissolution of feldspars and phyllosilicates. The dissolution of quartz is not ruled out but it should be a minor phenomenon. The precipitation of quartz may control the dissolved Si content during constant temperature leaching. During cooling from 100 to 50°C chalcedony, alumino-silicates, and chlorite are all capable of precipitation, possibly leading to some clogging or sealing of fissures.

Multi-packer hydraulic tests and radioactive tracer experiments carried out in boreholes in the Carnmenellis granite have shown that the flow of water through the rock is largely confined to narrow zones separated by zones of very low permeability. Correlation of the hydraulic data with geological data from oriented cores has shown that most of the flow is associated with discrete geological features, including pegmatitic and other veins, and elvan (quartz-feldspar porphyry) dykes, characteristic features of the granite of the area. Joints have also been found to conduct water, particularly in the upper 250 m of the granite. The permeability of the granite has been found not to be simply a function of fracture frequency, long sections of highly fractured rock having no associated flow under test conditions. While flow paths have been found to become less frequent with depth, flow rates do not vary over the depths studied, the highest flow rate recorded at the site being associated with a vein at 637 m. Water-conducting fractures have been found to have certain preferred orientations which vary with depth. A set striking 155°C is particularly well developed in the upper 250 m of the granite. This orientation is significant in that it is parallel to the cross-courses in the nearby mineralized belt with which the younger (Tertiary) mineralization tends to be associated and from which thermal brines issue into several local mines. These fractures are also approximately parallel to the maximum horizontal stress which affects the granite and which appears to be responsible for the selective opening of joints of certain orientations.

Diffusion into the rock matrix is potentially an important retardation mechanism for nuclides leached from an underground radioactive waste repository in a fractured hard rock. A technique for measuring the intrinsic diffusion coefficient and rock capacity factor is briefly described. Simple solutions to migration model equations are used, together with diffusion results and typical hydrogeological parameters, to estimate the impact of matrix diffusion on radionuclide migration. It is shown that retardation factors in excess of 100 and reductions in the peak concentration by 3–4 orders of magnitude are possible for non-sorbed ions, which would otherwise be carried by the flow and not retarded at all.

A sequence of sedimentary rocks from the Lower Chalk to the Oxford Clay has been studied as part of a reasearch programme into the feasibility of the disposal of low- and intermediate-level radioactive wastes in argillaceous strata. The preservation of aragonite in such rocks suggests that little groundwater movement has occurred through the bulk of these clays and this would imply that most groundwater movement is likely to occur along any fractures that may be present. Such fractures may interconnect with adjacent aquifer units along which most transport of radionuclides would occur. In these sediments the presence of smectitic clay minerals would strongly influence their retention of radionuclides by sorption and ion-exchange reactions. Compaction, calcite cementation, calcite dissolution and the diagenesis of biogenic silica have influenced the porosity and permeability of the rocks. These processes have also controlled the chemistry of many pore surfaces in contact with groundwater and these in turn will affect groundwater chemistry, and the nature of interactions with transported radionuclides.

Concentration, conductivity, temperature, and flow logs from sixteen brine-filled shafts in northern Germany have shown that the brines in all former potash salt mines exhibit a very sharp stratification into lower Mg-rich brine, an upper layer of Na-rich brine, and groundwater at the top. Laboratory experiments have shown that, at the MgCl2-brine/NaCl-brine boundary, both solutions become oversaturated with regard to NaCl, due to diffusion processes. NaCl therefore crystallizes from the solutions and forms a salt plug in the boundary region, which considerably reduces further diffusion. It is concluded that the observed effects would also take place in shafts. The backfilling material helps to nucleate the halite crystals and provides a structure on which they might be supported. The results of these experiments show that the density boundaries in the brine bodies act as barriers against transport of matter while the formation of a halite plug growing independently at the MgCl2/NaCl-brine interface acts as an additional barrier.

Studies of the U decay series (238U-234U-230Th) have been carried out on samples from unaltered bedrock and highly altered fracture/crush zones from drillcore Km3 (Kamlunge test-site). The fracture zones are characterized by abundant iron oxide coatings (hematite and hydroxy iron oxides) resulting from the passage of hydrothermal solutions coeval with the Lina granite intrusion. Enrichments of U and Th, thought to be due to co-precipitation (or preferential sorption) processes together with the iron-oxides, are also present.

The isotopic results show that out of a total of twelve rock samples measured, six indicate isotopic disequilibrium mostly due to unequal depletions of 234U and 238U; one near-surface sample indicated some minor assimilation of U. The major fracture zones generally indicate removal of total U. This has resulted from interaction with groundwaters which are still marginally oxidizing, even at depths of 375 m.

Isotopic disequilibrium has occurred within recent geological times, i.e. during the last 0.5 Ma as imposed by the half-lives of 234U and 230Th. In terms of radioactive disposal considerations, the results are important in that: (1) the investigated bedrock environment (100–500 m) is generally reducing; however (2) there is some evidence to indicate that rock/water interactions, leading to the removal of total U, have resulted from the presence of less reducing groundwaters within those large-scale fracture/crush zones which intersect the bedrock surface.

The first results of isotopic investigations as a part of the hydrogeological study of northern Switzerland are presented. This study is part of the global geological research project of the NAGRA (National Co-operative for the Storage of Radioactive Waste) which is intended to provide the scientific knowledge required for the assessment of the feasibility of safe disposal of highly radioactive waste in the geological formations of the area. The aim of the hydrogeological research programme is to assess the natural conditions in the sedimentary sequence and the underlying granite basement, by regional investigation of hydraulic parameters, isotopic composition, and hydrogeochemistry at all existing wells (boreholes and natural thermal springs) and in 11 to 12 deep-drilled boreholes (to final depth of 1500–2500 m).

Heat flow in SW England is well above average for the UK as a whole, but northwards towards Bath and Bristol the values decrease rapidly. However, hot springs occur both in the Bath-Bristol area and in mines in Cornwall. The development of hydrothermal circulation systems is thus not controlled entirely by geothermal gradient: the presence of a suitable fracture permeability is the main requirement. The thermal ‘head’ produced, which nevertheless depends upon the temperature and volume of water in the system, theoretically can exceed local topographic heads even in areas of low geothermal gradient.

Thermal groundwaters usually carry above average quantities of radioelements in solution because of the long residence times involved. 222Rn values are often particularly high. High concentrations of 222Rn in surface waters arise from the discharge of groundwater. The results of a survey of 222Rn in streams in SW England have established areas of high values which are interpreted as rising limbs of convection cells with dimensions in the order of 5–10 km.

In SE Devon γ-ray spectrometry of soils shows two E.-W. belts of high activity. The northern is coincident with the faulted southern margin of the Crediton Trough, while the southern is coincident with the westerly extension of the Abbotsbury fault system. Groundwater movement along deep-seated fracture systems is considered to be the explanation of these features. The horizontal scale of the area involved suggests that a thermal rather than local topographic head is the driving force. Groundwater circulation within fractures, driven by a thermal head, may therefore occur even in areas of low geothermal gradient and should be considered when selecting waste disposal sites.