P. Hölttä

The effects of matrix diffusion on radionuclide migration in rock column experiments

Rock column experiments were performed to examine the effects of matrix diffusion and hydrodynamic dispersion on the migration of radionuclides at the laboratory scale. Tritiated water and chloride transportation was studied in intact mica gneiss and in altered more porous tonalite columns with narrow flow channels. The column diffusion properties were estimated prior to water flow experiments using the gas diffusion method with helium as the tracer gas. The numerical compartment model for advection and dispersion, with and without matrix diffusion, was used to interpret the tracer transport in the columns. Matrix diffusion behavior was also distinguished from dominating hydrodynamic dispersion in rock column experiments at the slowest water flow rates.

Attempt to model laboratory-scale diffusion and retardation data

Different approaches for measuring the interaction between radionuclides and rock matrix are needed to test the compatibility of experimental retardation parameters and transport models used in assessing the safety of the underground repositories for the spent nuclear fuel. In this work, the retardation of sodium, calcium and strontium was studied on mica gneiss, unaltered, moderately altered and strongly altered tonalite using dynamic fracture column method. In-diffusion of calcium into rock cubes was determined to predict retardation in columns. In-diffusion of calcium into moderately and strongly altered tonalite was interpreted using a numerical code FTRANS. The code was able to interprete in-diffusion of weakly sorbing calcium into the saturated porous matrix. Elution curves of calcium for the moderately and strongly altered tonalite fracture columns were explained adequately using FTRANS code and parameters obtained from in-diffusion calculations. In this paper, mass distribution ratio values of sodium, calcium and strontium for intact rock are compared to values, previously obtained for crushed rock from batch and crushed rock column experiments. Kd values obtained from fracture column experiments were one order of magnitude lower than Kd values from batch experiments.

Determination of the elemental composition of copper and bronze objects by neutron activation analysis

A method for the elemental analysis of copper and bronze objects is described. Na, Co, Ni, Cu, Zn, As, Ag, Sn, Sb, W, Ir and Au are determined through instrumental neutron activation analysis. Mg, Al, V, Ti and Mn are determined after chemical separation using anionic exhange. The detection limits for a number of other elements are also given. Results for NBS standard reference materials are presented and the results compared with the recommended values. The agreement is good. The results of the analysis of five ancient bronze and two copper objects are presented.

Fracture flow and radionuclide transport in block-scale laboratory experiments

Summary Block-scale migration experiments were introduced to evaluate the simplified radionuclide transport concept used in assessing the safety of underground spent nuclear fuel repositories. The experiments were aimed to demonstrate visually the fracture flow, and to determine the hydraulic characteristics of a natural planar fracture and the transport behaviour of non-sorbing and sorbing radionuclides. For drill holes orthogonal to the fracture and equipped with injection or sealing packers flow rates in this study were measured as a function of hydraulic head. The outflow positions of water at each four side of the block were determined using uranine dye tracer. Tracer tests were performed using uranine, 99mTc and 22Na. Transport of a non-sorbing tracer through one of the flow channels was interpreted using an advection-dispersion model that on the generalised Taylor dispersion. Characterisation of the hydraulic properties of the fracture indicated that some drill holes were located in the region where the fracture was open and water conductive. No water conductivity was observed in two drill holes indicating closure of the fracture. Reasonably low flow rates obtained from three drill holes indicated their suitability for further radionuclide transport experiments. Elution times of technetium and uranine were fairly similar. Sodium was slightly retarded and was spread over a wider area than uranine and technetium. High water flow rates suggest that advective flow field dominated tracer transport. Experimental and calculated elution curves substantiate the suitability of our experimental set-up for further radionuclide transport experiments.

Na, Ca and Sr Retardation on Crushed Crystalline Rock

Different approaches for measuring the interaction between radionuclides and rock matrix are needed to test the compatibility of transport models and retardation experiments. In this work sorption of sodium (Na), calcium (Ca) and strontium (Sr) was studied on mica gneiss, unaltered, moderately altered and strongly altered tonalite samples taken from hole SY-KR7 drilled in the Syyry area in Sievi in western Finland. The mass distribution ratio values for sieved fractions were determined using static batch and thin section methods as well as crushed rock column method. Sodium, calcium and strontium sorption on mica gneiss and unaltered tonalite was slight and no difference due to fraction size was observed. Higher sorption and fair dependence on fraction size was obtained for altered tonalites owing to the composition of alteration minerals and larger specific surface areas. Difference in the Rd values between unaltered and altered rocks is partly the result of the higher specific surface areas for altered rocks, /{^-values calculated from thin section /{„-values and Rjvalues obtained from batch experiments were in good agreement. Except for sodium, Rvalues obtained from column experiments were lower but in agreement with Rvalues from batch and thin section experiments.

Radionuclide migration studies on tonalite

Migration of water, chloride, sodium, and calcium in tonalite was studied, using dynamic column and static through-diffusion methods. Autoradiography of rocks impregnated with {sup 14}C-methylmethacrylate was introduced in order to determine the spatial porosity distribution, as well as to identify and visualize the migration pathways of non-sorbing radionuclides in tonalite matrix as the mm-cm scale. The migration routes of sorbing radionuclides and the sorptive minerals in tonalite were determined by autoradiographic methods, using {sup 45}Ca as a tracer. Transport of radionuclides was interpreted, using models for hydrodynamic dispersion with diffusion into the rock matrix. In tonalite, porous minerals were distributed homogeneously in matrix and, therefore, retardation capacity of the rock matrix was found to be high.

The Effect of Specific Surface Area on Radionuclide Sorption on Crushed Crystalline Rock

The sorption of sodium ( 22 Na), calcium ( 45 Ca) and strontium ( 85 Sr) was studied on mica gneiss, unaltered, moderately altered and strongly altered tonalite samples taken from hole SY-KR7 drilled in the Syyry area in Sievi, Western Finland. The crushed rock samples were sieved into six fractions from 71 μm to 1250 μm. A proportional mineral composition for the different fractions were estimated by X-ray diffraction. The specific fraction surface areas were determined by the BET nitrogen adsorption method. The fractal method was applied to characterize rocks and to describe quantitatively surface irregularity. The mass distribution ratio values for each fraction were determined using the static batch method. The sorption of tracers onto different minerals was observed using rock thin sections. K d -values calculated from thin section K a -values and K d revalues obtained from batch experiments were in good agreement. Mass distribution ratios for different size fractions are given, and the effect of the specific surface area is discussed. Owing to larger specific surface areas considerably higher sorption on smaller fractions was found for altered tonalites.

Effect of Ionic Strength on the Stability of Colloids Released from Injection Grout Silica Sol

In Olkiluoto Finland colloidal silica called silica sol (EKA Chemicals) will be used as a non-cementitious grout for the sealing of fractures of the hydraulic apertures of 0.05 mm or less. The use of colloidal material has to be considered in the long-term safety assessment of a spent nuclear fuel repository. The potential relevance of colloid-mediated radionuclide transport is highly dependent on their stability in different geochemical environments. Objective of this work was to study the effect of ionic strength on stability of silica colloids released from silica gel. Silica gel samples were stored in contact with NaCl and CaCl 2 electrolyte solutions and in deionized water. Colloid release and stability were followed for two years by taking the samples after one month and then twice in a year. The release and stability of colloids were followed by measuring particle size, colloidal silica concentrations and zeta potential. The particle size distributions were determined applying the dynamic light scattering (DLS) method and zeta potential based on dynamic electrophoretic mobility. In dilute NaCl (10 -7 –10 -2 M) and CaCl 2 (3 10 -7 – 3 10 -3 M) solutions, a mean colloid diameter was less than 100 nm and high negative zeta potential values suggests the existence of stable silica colloids. After two years, the mean particle diameter was increased but it was still less than 500 nm and absolute value of zeta potential was decreased. In 0.1–1 M NaCl and 0.03–3 M CaCl 2 solutions, wide particle size distribution and zeta potential values around zero suggested particle aggregation and instable colloids. In deionized water, particle size remained rather stable and zeta potential remained high negative suggests stable silica colloids. The threshold value of ionic strength was 0.03–0.1 M when salinity had an effect on the stability of colloids. In Olkiluoto, the ionic strength of saline groundwater is order of magnitude higher than the range of effect value obtained in this study. Under the prevailing conditions in Olkiluoto, silica colloids are instable, but the possible influence of glacial melt waters has to be considered.