Martti Hakanen

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.

Simultaneous determination of 241Pu, 238Pu and 239,240Pu in low activity environmental samples

Abstract Studies on plutonium in the environment are mostly directed to the alpha emitting isotopes 238Pu and 239,240Pu. However, the largest contribution to the radioactivity of plutonium is due to the beta emitting isotope 241Pu. Plutonium was separated using anion exchange after leaching the 242Pu spiked sample with concentrated HNO3 and HCl. One aliquot of the eluate was spiked with an additional plutonium tracer, 236Pu, and electrodeposited for alpha spectrometric determination of 238Pu and 239,240Pu in the sample and for the determination of chemical recovery in the solution before electrodeposition. The activity of 241Pu was measured in the second aliquot using a calibrated liquid scintillation counter. For quench correction, the external standard channels ratio method was applied. The counting efficiency of 241Pu was about 35% and the lower limit of detection with a counting time of 120 min was 1 pCi (37 mBq). The concentration of 241Pu in lichen was about 3000 and 800 pCi/kg in 1964 and 1970, respectively and 2.5 pCi/kg in reindeer liver in 1977. The maximum activity ratio of 241Pu to 239,240Pu, about 16, in 1965 is in good agreement with that given for fresh fallout.

Radionuclide transport and retardation in rock fracture and crushed rock column experiments

Transport and retardation of non-sorbing tritiated water and chloride and slightly sorbing sodium was studied in Syyry area SY-KR7 mica gneiss, in altered porous tonalite and in fresh tonalite. Experiments were performed using dynamic fracture and crushed rock column methods. Static batch method for sodium was introduced to compare retardation values from static and dynamic experiments. The 14C-PMMA method was used to study the pore structure of matrices. The pore aperture distribution was evaluated from Hg-porosimetry determinations and the surface areas were determined using the B.E.T. method. The flow characteristics and transport behavior of tracers were interpreted using a numerical compartment model for dispersion. The effect of matrix diffusion was calculated using an analytical solution to the advection-matrix diffusion problem in which surface retardation was taken into account. Radionuclide transport behavior in rock fractures was explained on the basis of rock structure.

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.

Modeling of cesium sorption on biotite using cation exchange selectivity coefficients

Abstract For the modeling of cesium sorption on biotite, samples of natural biotite separated from gneissic rocks were converted into monoionic potassium, sodium, and calcium forms, and sorption isotherms for Cs/K, Cs/Na and Cs/Ca exchange were determined at pH 6 and 8 in E-4–E-8 M Cs solutions. Selectivity coefficients for Cs/K, Cs/Na, and Cs/Ca ion exchange reactions were calculated from the isotherm data, using the Gaines-Thomas convention. At Cs loadings below 1% of the total ion exchange capacity, the overall selectivity coefficient for Cs/Ca exchange was approximately five and seven orders of magnitude higher than those for Cs/Na and Cs/K exchange, respectively. Based on the selectivity coefficients, the ion exchange isotherms were modeled with the U.S. Geological Survey PhreeqC program, assuming three different types of ion exchange site: sites on the basal planes on biotite crystal surfaces with 95% site abundance, probable interlayer sites on crystal edges [frayed edge sites (FESs)] (0.02%) and third-type sites (5%), the physical background of which is unclear. Of these three types, the FES sites were superior in Cs selectivity, while the planar sites exhibited the lowest selectivity, and the third-type sites had selectivity between these two. The functionality of the model was successfully verified by modeling the Cs sorption isotherms on crushed mica gneiss rock in saline groundwater. Determination of the exchangeable ions K, Na, Ca, and Cs on the basal plane and edge surfaces by scanning electron microscopy-energy-dispersive x-ray spectroscopy (SEM-EDX) supports the results of modeling: edge sites highly prefer Cs ions and also Ca and Na ions but not K ions.

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.

Sorption of cesium on boreal forest soil I: the effect of grain size, organic matter and mineralogy

The sorption of cesium was studied using humus and mineral soil samples. The effect of grain size, soil depth, organic matter and mineralogy were evaluated. The smallest grain size showed the highest sorption whilst it was rather equal for larger grains sizes. The sorption of cesium increased with soil depth being the lowest in the humus. Among the mineral soil layers the highest retention was found in the layer enriched with clay fraction. Muscovite retained cesium fairly well in pure water and model soil solution. Quartz showed the poorest sorption in both solutions.

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.

Sorption of niobium on boreal forest soil

Abstract The sorption of niobium (Nb) was investigated on humus and mineral soil samples taken from various depths of a four-metre deep forest soil pit on Olkiluoto Island, southwestern Finland. Mass distribution coefficients, Kd, were determined in batch sorption tests. The steady state of Nb sorption was observed in the mineral soil samples already after one week of equilibration, and sorption decreased with depth from a very high value of 185000 mL/g at 0.7 m to 54000 mL/g at 3.4 m. The reason behind this decrease is probably the tenfold reduction in the specific surface area of the soil at the same depth range. Distribution coefficients were clearly lower in the humus layer (1000 mL/g). The Kd values determined in pure water at a pH range of 4.7–6.5 were at a high level (above 55000 mL/g), but decreased dramatically above pH 6.5, corresponding to the change in the major Nb species from the neutral Nb(OH)5 to the low-sorbing anionic Nb(OH)6− and Nb(OH)72−. However, the Kd values in the model soil solution were in the slightly alkaline range an order of magnitude higher than in pure water, which is probably caused by the formation of calcium niobate surface precipitate or electrostatic interaction between surface-sorbed calcium and solute Nb. Among nine soil constituent minerals kaolinite performed best in retaining Nb in both pure water and model soil solution at pH 8, whereas potassium feldspar showed the poorest sorption. The Kd value for kaolinite was above 500000 mL/g in both solutions, while the respective potassium feldspar values were in the range of 120–220 mL/g.

Modelling of niobium sorption on clay minerals in sodium and calcium perchlorate solutions

Abstract The sorption behaviour of niobium on kaolinite and illite minerals in sodium and calcium perchlorate solutions was evaluated with use of the mass distribution coefficient, Rd, obtained in batch sorption experiments. Very high distribution coefficient values, about 100 m3/kg, were obtained for both minerals in the neutral pH range between 6 and 8. Values were somewhat lower at pH 5. In NaClO4 solution, the sorption of niobium starts to decrease at pH higher than 8. This is in agreement with the increase, with pH, in the proportion of anionic niobate species, which are presumed to be low or non-sorbing. A similar decrease was not observed in Ca(ClO4)2 solution, probably owing to the influence of Ca on niobium solution speciation and surface species. The surface complexation model was applied to model the Rd values. The model fitted well for the NaClO4 solution but only at pH below 9 for the Ca(ClO4)2 solution. The discrepancy between the strong sorption of niobium in calcium-bearing solution at high pH and the calculated speciation is due in part to the non-inclusion of calcium niobate solution species and Ca-Nb compounds in the present NEA and other similar thermodynamic databases.