Pretreated inactive ion exchange resins from the Loviisa nuclear power plant (NPP) were first reduced to one tenth of the original volume through microbiological treatment. During the process, the granular ion exchange resins were decomposed to result in dregs, which were solidified with two types of Portland cements. The objective of the present experiments was to investigate whether commercial cements are suitable solidification agents for this kind of waste.

A total of ten mixtures were pretested for their rheological and setting properties. On the basis of the pretest results, four additional mixtures were chosen and tested for the spread value, density, air content, setting time and bleeding of the fresh waste product and for the dimensional stability and compressive strength of the hardened waste product. The cementing systems incorporated in the tests were ASTM type V Portland cement and ASTM type P Portland Composite cements. The dregs used in the tests were taken from a Pilot-Plant experiment at the Loviisa NPP and contained 2 wt-% solids.

The test results were promising in showing that microbiological dregs can very easily be solidified with Portland cements to form a high-quality waste product. Thus, the microbiological treatment of spent ion exchange resins will drastically decrease the amount of solidified waste to be disposed of at the Loviisa NPP.

The repassivation potential, ER, for metal/metal-crevice of Commercially Pure Titanium, C.P.Ti, was determined in NaC1 solutions at temperatures up to 250C. The ER has its least noble value near 100C and becomes more noble as the temperature increases. As shown in previous research[1], the shrinkage of the repassivation region should continue with increasing temperatures. However, in conducting this same experiment at temperatures higher than 100C, an examination of the NaCI concentration - temperature - crevice corrosion map verifies that the repassivation region began to expand again when the temperature exceeded 140C. This expansion continued as the temperature continued to increase.

The corrosion behavior of type 304 stainless steel was studied under gamma irradiation as part of the evaluation for the long-term durability of high-level radioactive waste (HLW) disposal containers. Gamma rays, generated from fission products in high-level radioactive waste, are considered to change the environment around the canisters and overpacks. The redox potentials for NaCl solutions and corrosion potentials of stainless steel were measured to consider the effects of gamma irradiation, by using an electrochemical method. The pitting potentials of stainless steel for NaCl solutions were also measured to examine the pitting corrosion under gamma irradiation. As a result of this experiment, it is concluded that the oxidizing properties as a result of the formation of H2O2 and H2 produced by gamma irradiation depended on the concentration of Cl−, and that the strength of oxidizing properties of 1M (mol·dm−3) NaCl solution was particularly high. and the pitting corrosion was found for 1M NaCI solution under gamma irradiation at the dose rate of 2.6×102 C/kg·h (1.0×106 R/h) at 60°C, by using an electrochemical method.

In addition to mild steel, several stainless alloys are being proposed as materials for packages for geological disposal of high-level nuclear waste. When buried deep underground, the greatest detriment to the integrity of packages made of these alloys is localized corrosion, for which critical conditions for initiation of crevice corrosion in chloride environments, with or without other ions, need be precisely known.

Crevice corrosion behavior of Type 304 stainless steel, Type 316 stainless steel, Alloy 825, Ti-Gr.1, and Ti-Gr.12 in solutions containing ions of chloride, bromide (these two for their ordinary presence in natural waters), or thiosulphate (this for the likelihood of microbially influenced corrosion) to varying concentrations have been empirically examined. All of these alloys exhibit much the same concentration dependency of crevice corrosion sensitivity for chloride and bromide ions, while Type 304 stainless steel is particularly sensitive to the thiosulphate ion. The region of insensitivity for chloride ion is wider in the increasing order of Type 304 stainless steel, Type 316 stainless steel, Ti-Gr. 1, and Ti-Gr. 12, with that of Alloy 825 lying somewhere in between.

In the current design of geological disposal of high-level nuclear waste, the use of bentonite to stand as an artificial barrier-cum-buffer between the host rock and the packages made of mild steel is being investigated. Although mild steels commomly have been considered to be passivity in alkaline environments, under certain circumstances, they become liable to localized corrosion, e.g., pitting corrosion and crevice corrosion. Since bentonite can turn the environment alkaline to a pH of approximately 10 when it is mixed with groundwater, critical conditions for the initiation of localized corrosion of mild steel must be known to evaluate the extremely long time integrity of disposal packages serving in such an environment. This paper presents and discusses the observations and results acquired in a series of critical conditions for the initiation of localized corrosion of mild steels in various groundwater-bentonite environments at 20C, with a deaerated aqueous solution of 1 mMol/L [HCO3−] +10 ppm [CI−], simulating the natural groundwater and varying the bentonite content.

The design-basis, defense-related, transuranic waste to be emplaced in the Waste Isolation Pilot Plant may, if sufficient H2O, nutrients, and viable microorganisms are present, generate significant quantities of gas in the repository after filling and sealing. We summarize recent results of laboratory studies of anoxic corrosion and microbial activity, the most potentially significant processes. We also discuss possible implications for the repository gas budget.

The study of microbiologically influenced corrosion (MIC) has progressed from phenomenological case histories to a mature interdisciplinary science including electrochemical, metallurgical, surface analytical, microbiological, biotechnological and biophysical techniques. With gene probes and microelectrodes it is now possible to measure interfacial dissolved oxygen, dissolved sulfide and pH and to further determine the microbial species responsible for the localized chemistry. Biofilms can be tailored to contain consortia of specific microorganisms and naturally occurring biofilms can be dissected into cellular and extracellular constituents. Scanning vibrating electrodes can be used to map the distribution of anodes and cathodes so that localized corrosion can be correlated with the location of microorganisms. The development of environmental scanning electron, atomic force, and laser confocal microscopy makes it possible to image cells on surfaces and to accurately determine the spatial relationship between microorganisms and corrosion. Transport of nutrients through biofilms is being modeled using techniques including optical density measurements to precisely locate the water/ biofilm interface and nuclear magnetic resonance imaging to visualize flow characteristics near surfaces colonized with microorganisms. The ways in which these new techniques can be used to understand fundamental mechanisms and to discriminate critical issues of MIC will be discussed.

Microbiologically influenced corrosion (MIC) is the term used for the phenomenon where corrosion is initiated or accelerated by microorganisms. Biofilms of bacteria form on metal surfaces when exposed to natural waters. The activity of these biofilms and how they attach themselves to metal surfaces directly influence corrosion mechanisms.

This paper describes the mechanisms for MIC and the factors which influence the susceptibility of austenitic stainless steel weidments to MIC. The metallurgical, microbiological and electrochemical factors that influence MIC are discussed. Case histories of MIC-related failures and field test results of austenitic stainless steel weldments in various welded conditions are presented.

Current field experience with microbiological influenced corrosion (MIC) has now extended into the medium-grade stainless steels containing 4% molybdenum and in excess of 20% chromium. These may indeed be special cases where a combination of synergistic effects, temperature, and wet-dry cycles have aggravated a situation that is already subject to a mild form of MIC. Data are presented from a fresh water field site, comparing the relative performance of several welded coupons, including AISI 304L, 316L, and higher alloyed grades, 622, C276, C-22, 25-6Mo exposed to principally iron-oxidizing bacteria. Specific data is also presented from a saltwater laboratory study of AISI 316/E308 welds where sulfate-reducing bacteria were included. Normally this weld configuration is considered “mismatched” however has nevertheless been employed at several inland power stations. Data is presented which suggests that under “freshwater” conditions (ie. < 150 ppm Cl−) excluding deposits originating from other sources, for example, calcareous scales, an increase in chromium content may significantly reduce the problem. The laboratory study showed that severe generalized rusting of 316/E308 welds may be expected in the presence of fermentative and sulfate-reducing bacteria in chloride environments. The relationship of these data, and of those available in the literature, to the problem of long-term radioactive waste disposal, is discussed with respect to materials selection.

Ultra thin films (12nm) were sputter deposited onto cylindrical germanium internal reflection elements pre-coated with a thin (2nm) layer of Cr2O3. Two crystals were inserted into Circle cell flow-through chambers and mounted on the optical bench of an Fourier Transform Infrared (FT-IR) spectrometer. One chamber was maintained as a sterile control while the other was sequentially inoculated with four bacterial species: Pseudomonas aeruginosa, Bacillus subtillis, Hafnia alvei, and Desulfovibrio gigas, in that order. The water absorption band (1640cm−1) was monitored and used to follow the deterioration of the ultra thin films. In this respect, the sterile control and inoculated films exhibited only slight differences during the 1000h course of the experiment. Assay of the visible biofilm that had accumulated on the surface of the inoculated crystal after 1000h revealed that the film incorporated viable cells from all four strains.

Analytical and conceptual deficiencies in understanding compositional variability in the smectite clays are expected to generate uncertainty in models used to simulate the chemical environment in bentonite backfill. Equilibrium models accounting for nonstoichiometry in smectite can nevertheless bound ranges in aqueous solution compositions that are an explicit function of the uncertainty in smectite compositions. In one approach, we quantify uncertainty in terms of ranges in concentrations of octahedral and tetrahedral Al, and exchange-site cations and vacancies. Heterogeneous mass transfer in bentonite-water systems is modeled using conventional mass-action relations and standard Gibbs energies for stoichiometric minerals, and the site-occupancy constraints combined with site-mixing relations for smectite. The resultant bounding conditions in groundwater compositions may be large or small depending on which aqueous species are of interest in a given situation, but they are valid irrespective of whether equilibrium in smectite-water reactions is attained or is inhibited by slow intracrystalline reaction rates.

Aqueous diffusion coefficients have been experimentally determined in a variety of porous/fractured geologic and engineered media. For performance assessment applications, the purely diffusive flux must be separated from retardation effects. The simple diffusion coefficient, D, does not include any transient chemical effects, e.g., sorption, which lower the diffusion coefficient for some finite time period until equilibrium is reached. D is primarily a function of volumetric water content, θ, and not material characteristics. At high water contents, D gradually declines as water content decreases, from 10−5 cm2/sec at θ ∼ 50% to 10−7 cm2/sec at θ ∼ 5%, followed by a sharp decline to 10−10 cm2/sec at θ ∼ 0.5%. Although surface diffusion has a strong experimental basis in the transport of gases along metal surfaces, experimental evidence for aqueous geologic/backfill/engineered systems strongly indicates that surface diffusion is not important, even in bentonite, because of the extremely poor connectivity among electric double-layers and the extremely low diffusivities and high ∂C/∂x at small area/point contacts which more than negate the increased flux along intragrain surfaces.

The apparent diffusion coefficients were measured at room temperature (about 23°C) under atmospheric condition by the one-dimensional non-steady state diffusion method for 3H, 99Tc, 137Cs, 237Np and 241Am in compacted sodium-bentonite saturated with water. Sodium-bentonite, which is commercially available as KunigelVl®, was used in this study. Experiments were carried out in the density range of 0.4–2.0 (×103kg/m3). Bentonite in the cell was prepared to be saturated with distilled water. The measured apparent diffusion coefficient decreases with increasing dry density of bentonite. That the apparent diffusion coefficient of 3H decreased as a function of dry density of bentonite appears to be the effect of the change of porous structure with dry density of bentonite. 99Tc may be retarded by anion-exclusion because dominant diffusion specie of 99Tc is pertechnetate ion under atmospheric condition. Retardation for 137Cs may be caused by ion-exchange on bentonite. The sorption, anion-exclusion and molecular filtration are considered as a retardation mechanism for 237Np and 241Am because those dominant species are negatively charged and of large ionic size.

In this study the diffusion of uranium dissolved from uranium oxide fuel was studied experimentally in compacted sodium bentonite (Wyoming bentonite MX-80). The parameters varied in the study were the density of bentonite, the salt content of the solution and the redox conditions. In the studies with non-saline water of total dissolved solids about 300 ppm, uranium was both in aerobic and anaerobic experiments as anionic complexes and followed the anionic diffusion mechanism. Anion exclusion decreased effective diffusion coefficients, especially in more dense samples. In the studies with saline water of total dissolves solids about 35000 ppm, uranium appeared in the aerobic experiments probably as cationic complexes and followed the cationic diffusion mechanism. Uranium in the saline, anaerobic experiment was probably U(OH)4 and followed the diffusion mechanism of neutral species.

Several series of one-dimensional tests were used to investigate the nature of transient heat and moisture movements in a clay buffer under different imposed temperature gradients. The measured temperature and moisture profiles were used to calculate the diffusion parameters governing heat and moisture movement in the buffer material. The diffusion parameters are shown to depend on the moisture content, temperature and moisture equilibrium time.

Water vapor adsorption characteristics of buffer materials to be used for the geologic disposal of high-level radioactive waste have been investigated. Highly compacted blocks of Japanese Na bentonite were used as the buffer material. Initial dry density of the blocks was 1.8 g/cm3. Volume changes and water contents of the blocks in equilibrium with surrounding moist air were measured. The humidity of the surrounding air was kept constant, and the suction of the block at equilibrium has been determined by the humidity. The temperature of the surrounding air was varied between 20°C and 60°C.

The volumetric strain was observed to vary approximately between −3% and 13% depending on the humidity of 0.6% to 95%. Some analytical expressions derived from these experiments on moisture adsorption are presented in this paper. Water vapor adsorption isotherm of the bentonite blocks was also obtained. The swelling pressures calculated from the analytical expressions are compared with literature data for this bentonite.

Gas generation due to alpha particle deposition was investigated in four WIPP relevant brines; WIPP brine A, ERDA-6, DH-36 and G8-B. This was done by spiking each brine with plutonium-239 and periodically sampling the gas phase to determine the nature of the gaseous products and the rates of gas generation. The predominant gas generated radiolytically was hydrogen, with yields ranging from 0.6 to 1.5 molec/100 eV for the four brines tested. Plutonium (VI) was stable in two synthetic brines, WIPP brine A and ERDA-6 but was rapidly reduced in the underground collected brines DH-36 and G8-B, although most of the plutonium remained in solution.

The evolution of impure rocksalt samples under irradiation has been investigated and compared to the evolution of pure halite, concerning the radiolytic release of gases. Four different types of rocksalt (pure halite, anhydrite-bearing, sylvinite-bearing, and marneous) have been irradiated with spent fuel at doses ranging from 104Gy to 107Gy, under synthetic air or helium at 50°C, 150°C, and 200°C. Marneous and anhydrite-bearing salt produced higher amounts of gas than the two other types, especially for H2, CO, and CH4. Radiolytic gas production essentially originates from the decomposition of traces of different kind of impurities : fluid inclusions, which can be composed of brine and/or organic fluids and gases; minerals such as carbonates, sulfates, or hydrated minerals; organic matter, in general (kerogen). Pure halite decomposes only at very high doses (more than 107Gy) giving off some Cl2 and other corrosive gases. Gas production increases steadily with dose for H2, CO, and CH4, contrary to what is observed for the pure Asse salt, where H2 and CO, respectively, peak at 106, and 105 Gy. The increase, with dose, in the production of CH4, C2H6, and C3H8 is far higher for marneous salt and higher for anhydrite-bearing salt. The decrease of the O2/N2 (oxygen consumption) ratio in the irradiation atmosphere is in the following order: marneous>anhydrite>halite=sylvinite. The overall effect of γ-irradiation on impure rocksalt can be described as follows : destruction of organic matter that produces chemically reduced gases (H2, CO, hydrocarbons), after an initial stage of oxygen consumption, which is reached more or less quickly, depending on the availability and quantity of organic matter. The use of impure, i.e, organic matter-bearing salt, as host-rock or engineered barrier for nuclear wastes, may be questioned, because of the high amount of gases produced in the immediate vicinity of the container (explosion hazards, pressure build-up). The present study will be followed by a modelling of the in-situ radiolytic gas production, taking into account: 1) the dose distribution with time, 2) the temperature distribution with time, and 3) the geometry of the repository, and will allow us to estimate the potentiel safety impact of radiolytic gas production in the case of a repository emplaced in impure rocksalt.