Cantilever-enhanced photoacoustic measurement of HTO in water vapor

A photoacoustic detection of tritiated water (HTO) is presented. The method uses cantilever-enhanced photoacoustic spectroscopy (CEPAS) to reach sub-ppb sensitivity for HTO in the gas phase. A noise equivalent concentration of 0.88 ppb is reached with a sampling time of 1 min. The high performance and small sample volume of CEPAS allows sensitive detection of HTO from a sample with low total activity.Peer reviewe

Development and application of an advection-dispersion model for data analysis of electromigration experiments with intact rock cores

An advection-dispersion model was developed for interpreting the experimental results of electromigration in granitic rock cores. The most important mechanisms governing the movement of the tracer ions, i.e. electromigration, electroosmosis and dispersion were taken into account by the advection-dispersion model, but the influence of aqueous chemistry was ignored. An analytical solution in the Laplace domain was derived and then applied to analyze the measured results of a series of experiments, performed in an updated device with different applied voltages. The modelling results suggested that both studied tracers, i.e. iodide and selenite, are effectively non-sorbing in the intact rock investigated. The effective diffusivities and formation factors evaluated from the model were also found to be in good agreement with data reported in literature and the associated uncertainties are much smaller than those obtained from the classical ideal plug-flow model, which accounts only for the dominant effect of electromigration on ionic transport. To explore further how the quality of parameter identifications would be influenced by neglect of aqueous chemistry, a reactive transport model was also implemented, which may be regarded as a multi-component version of the advection-dispersion model. The analysis showed that the advection-dispersion model works equally well as the reactive transport model but requires much less computational demanding. It can, therefore, be used with great confidence to interpret the experimental results of electromigration for studies of diffusion and sorption behavior of radionuclides in intact rock cores.Peer reviewe

Uranium Migration in Crystalline Rocks

The mechanisms controlling the migration of uranium in crystalline rocks such as granites or granodiorites are insufficiently well understood to arrive at a quantitatively defensible safety case for deep disposal of radioactive waste. To help further our knowledge of the relevant processes, a controlled column experiment was undertaken using a disc of metallic (depleted) uranium as a source and granodiorite samples from a former candidate disposal site for spent uranium fuel, Sievi in Finland, as the host medium. The experiment ran for approximately 500 days. This report summarises efforts made to simulate the uranium migration observed during the experiment. The model was developed from blind predictions to an inverse model that attempted to reproduce the measured effluent data. In the absence of independently derived kinetic data for uranium precipitation and dissolution it is difficult to arrive at a truly unique solution. Nevertheless, the exercise has been instructive in highlighting the principal areas of uncertainty and the pit falls that await those seeking to represent far more complex hydrogeochemical systems than that investigated here.JRC.F.7-Energy systems evaluatio

Radium sorption on biotite; surface complexation modeling study

The sorption of Ra on Olkiluoto biotite in the context of deep geological disposal of spent nuclear fuel was studied with isotherm batch sorption experiments. Ba was used as an analog for Ra in the experiments and modeling studies. A wide concentration range of Ra/Ba was used in the isotherm studies (2.6 x 10(-9) M to 1 x 10(-3) M) in addition to four different Olkiluoto reference groundwaters with salinity types ranging from fresh to saline. Experimental results show that both in the fresh and saline reference groundwaters, the distribution coefficients of Ra tend to decrease in the higher isotherm concentrations of Ba. With one reference groundwater, the distribution coefficients increased with the concentration of Ba due to significant coprecipitation of Ra. With the fresh reference groundwaters, the distribution coefficients of Ra were consistently approximately one order of magnitude lower than in the saline reference groundwater. A PHREEQC multi-site complexation model coupled with an optimization tool in Python was used to interpret the experimental Ra sorption results. Molecular modeling with CASTEP code implemented into Materials Studio was used to update the PHREEQC model with more realistic biotite sorption site density data. It was observed that while the multi-site model predicts the sorption of Ra well in lower isotherm concentrations, auxiliary reactions of Ra disrupt the model in high Ba isotherm concentrations. The experimental and modeled distribution coefficient data of Ra on biotite can be used in the safety case calculations of the deep geological disposal of spent nuclear fuel in Finland and Sweden.Peer reviewe

STED nanoscopy : A novel way to image the pore space of geological materials

STED nanoscopy (Stimulated Emission Depletion). which can resolve details far below the diffraction barrier has been applied hitherto preferentially to life sciences. The method is however also ideal for the investigation of geological matrices containing transparent minerals, an application tested here, to our knowledge, for the first time. The measurements on altered granitic rock and sedimentary clay rock, both containing very fine-grained phases, were conducted successfully. The STED fluorophore was dissolved in C-14-labelled methylmethacrylate (C-14-MMA) monomer which was polymerised within the rock matrix, thereby labelling the pore space in the geomaterials. Double labelling provided by the C-14-labelled MMA enables autoradiography and scanning electron microscopy (SEM), providing necessary complementary information for characterisation and quantification of porosity distributions and mineral and structure identification. Promising perspectives for further investigations of geological matrices by using different fluorophores and the optimisation of measuring procedures or even higher resolution are discussed. The combination of these different methods enlarges the observation scale of porosity from nanometre to centimetre scale.Peer reviewe

Sealing, healing and fluid flow in clay rocks : Insights on episodic flow events in fault zones

The porosity distribution and mineralogical changes in a clay-rich fault core from the Tournemire underground research laboratory are analyzed to determine the mechano-chemical processes in a small-scale vertical strike-slip fault. The results display significant spatial variations in porosity and mineralogy along different gouge zones due to a polyphased tectonic history combined with complex paleo-fluid migrations. Porosity values increase from the center of the gouges to their borders indicating diffusive sealing/healing effects and past hydrothermal activities. The healing and thus the strengthening of the fault is marked by an increase of calcium content, which is concurrent with lower porosities around the gouge zone. Chemical mapping in the gouges reveal clay alteration, iron zonality and the presence of zinc sulphide as well as barium sulphate inside the gouge, further suggesting past hydrothermal activity. Finally, even though the observed porosity variations only occur in subcentimeter-thick gouge bands, the higher porosity sections are pathways for fluid flow during fault activity. © 5th International Conference on Fault and Top Seals 2019. All Rights Reserved.Peer reviewe

Diffusion and Sorption Studies of Cs, Sr and Co in Intact Crystalline Rock

Three cationic tracers, Sr2+, Co2+ and Cs+ were tested with a modified electromigration device by applying 2V, 3V and 4V voltage gradients over an intact Grimsel granodiorite rock sample. An ideal plug-flow model and an advection-dispersion model were applied to analyze the breakthrough curves. Matrix characterization by C-14-PMMA autoradiography and scanning electron microscopy showed that in the centimeter scale of Grimsel granodiorite rock, the interconnected matrix porosity forms a well-connected network for diffusion. Micrometer-scale fissures are transecting biotite and chlorite minerals, indicating sorption of the studied cations. The ideal plug-flow model indicated that the effective diffusion coefficients (De values) for Sr2+, Co2+ and Cs+ tracer ions within the Grimsel granodiorite rock were 3.20 × 10−13 m2/s, 1.23 × 10−13 m2/s and 2.25 × 10−12 m2/s, respectively. De values were also derived from the advection-dispersion model, from which 2.86 × 10−13 m2/s, 1.35 × 10−13 m2/s and 2.26 × 10−12 m2/s were calculated. The diffusion speed for the tracers was in the sequence of Cs+ > Sr2+ > Co2+ that is in the same sequence as their diffusion in diluted water. The distribution coefficients (Kd values) calculated from the models covered the range of two magnitudes (from 10−7 m3/kg to 10−5 m3/kg). The result indicated that the sorption process of the studied elements did not reach equilibrium during the electromigration process, mainly due to the too much acceleration of the migration speed by the voltage gradients applied over the rock sample

Diffusion and Sorption Studies of Cs, Sr and Co in Intact Crystalline Rock

Three cationic tracers, Sr2+, Co2+ and Cs+ were tested with a modified electromigration device by applying 2V, 3V and 4V voltage gradients over an intact Grimsel granodiorite rock sample. An ideal plug-flow model and an advection-dispersion model were applied to analyze the breakthrough curves. Matrix characterization by C-14-PMMA autoradiography and scanning electron microscopy showed that in the centimeter scale of Grimsel granodiorite rock, the interconnected matrix porosity forms a well-connected network for diffusion. Micrometer-scale fissures are transecting biotite and chlorite minerals, indicating sorption of the studied cations. The ideal plug-flow model indicated that the effective diffusion coefficients (De values) for Sr2+, Co2+ and Cs+ tracer ions within the Grimsel granodiorite rock were 3.20 × 10−13 m2/s, 1.23 × 10−13 m2/s and 2.25 × 10−12 m2/s, respectively. De values were also derived from the advection-dispersion model, from which 2.86 × 10−13 m2/s, 1.35 × 10−13 m2/s and 2.26 × 10−12 m2/s were calculated. The diffusion speed for the tracers was in the sequence of Cs+ > Sr2+ > Co2+ that is in the same sequence as their diffusion in diluted water. The distribution coefficients (Kd values) calculated from the models covered the range of two magnitudes (from 10−7 m3/kg to 10−5 m3/kg). The result indicated that the sorption process of the studied elements did not reach equilibrium during the electromigration process, mainly due to the too much acceleration of the migration speed by the voltage gradients applied over the rock sample