Treatment of boundary conditions in through-diffusion: A case study of (85)Sr(2+) diffusion in compacted illite.

Valuable techniques to measure effective diffusion coefficients in porous media are an indispensable prerequisite for a proper understanding of the migration of chemical-toxic and radioactive micropollutants in the subsurface and geosphere. The present article discusses possible pitfalls and difficulties in the classical through-diffusion technique applied to situations where large diffusive fluxes of cations in compacted clay minerals or clay rocks occur. The results obtained from a benchmark study, in which the diffusion of (85)Sr(2+) tracer in compacted illite has been studied using different experimental techniques, are presented. It is shown that these techniques may yield valuable results provided that an appropriate model is used for numerical simulations. It is further shown that effective diffusion coefficients may be systematically underestimated when the concentration at the downstream boundary is not taken adequately into account in modelling, even for very low concentrations. A criterion is derived for quasi steady-state situations, by which it can be decided whether the simplifying assumption of a zero-concentration at the downstream boundary in through-diffusion is justified or not. The application of the criterion requires, however, knowledge of the effective diffusion coefficient of the clay sample. Such knowledge is often absent or only approximately available during the planning phase of a diffusion experiment.

Quantitative chemical imaging of element diffusion into heterogeneous media using laser ablation inductively coupled plasma mass spectrometry, synchrotron micro-X-ray fluorescence, and extended X-ray absorption fine structure spectroscopy.

Quantitative chemical imaging of trace elements in heterogeneous media is important for the fundamental understanding of a broad range of chemical and physical processes. The primary aim of this study was to develop an analytical methodology for quantitative high spatial resolution chemical imaging based on the complementary use of independent microanalytical techniques. The selected scientific case study is focused on high spatially resolved quantitative imaging of major elements, minor elements, and a trace element (Cs) in Opalinus clay, which has been proposed as the host rock for high-level radioactive waste repositories. Laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS), providing quantitative chemical information, and synchrotron radiation based micro-X-ray fluorescence (SR-microXRF), providing high spatial resolution images, were applied to study Cs migration into Opalinus clay rock. The results indicate that combining the outputs achievable by the two independent techniques enhances the imaging capabilities significantly. The qualitative high resolution image of SR-microXRF is in good agreement with the quantitative image recorded with lower spatial resolution by LA-ICPMS. Combining both techniques, it was possible to determine that the Opalinus clay sample contains two distinct domains: (i) a clay mineral rich domain and (ii) a calcium carbonate dominated domain. The two domains are separated by sharp boundaries. The spatial Cs distribution is highly correlated to the distribution of the clay. Furthermore, extended X-ray absorption fine structure analysis indicates that the trace element Cs preferentially migrates into clay interlayers rather than into the calcite domain, which complements the results acquired by LA-ICPMS and SR-microXRF. By using complementary techniques, the quantification robustness was improved to quantitative micrometer spatial resolution. Such quantitative, microscale chemical images allow a more detailed understanding of the chemical reactive transport process into and within heterogeneous media to be gained.

A high-resolution abrasive method for determining diffusion profiles of sorbing radionuclides in dense argillaceous rocks.

The diffusion of (134)Cs(+) and (22)Na(+) in Opalinus Clay (OPA) was studied by in-diffusion laboratory experiments. The diffusive tracer profiles in the rock were determined using a high-resolution abrasive peeling method. The radionuclide activities in the grinding swarf were measured directly via gamma-spectrometry. By choosing the appropriate abrasive paper, a resolution down to 15 microm can be achieved. This is important when analysing strongly sorbing radionuclides such as tri- and tetravalent actinides that show steep, shallow diffusion profiles. In this study, a resolution between 20 and 90 microm was obtained which was sufficient for a good spatial resolution of the diffusion profiles. Both the effective diffusion coefficients and the distribution coefficients of the radionuclides could be determined by applying a single reservoir with decreasing source concentration analysis for a semi-infinite case. In the case of (22)Na(+), effective diffusion coefficients of D(e)=2.0 x 10(-11)m(2)s(-1) and D(e)=1.5 x 10(-11)m(2)s(-1) for Benken (Zurcher Weinland) OPA and Mont Terri OPA, respectively, were derived. The distribution coefficients were K(d)=3.1 x 10(-4) and 0.9 x 10(-4)m(3)kg(-1), respectively. For (134)Cs(+) the effective diffusion coefficients were higher, i.e. D(e)=3.1 x 10(-11)m(2)s(-1) for OPA from Benken and D(e)=3.0 x 10(-11)m(2)s(-1) for OPA from Mont Terri. The distribution coefficients determined were K(d)=0.16 m(3)kg(-1) for Benken and 0.23 m(3)kg(-1) for Mont Terri. Comparison of the data obtained for the weakly sorbing (22)Na(+) with those from earlier through-diffusion experiments showed that there is good agreement between the two methods. In the case of (134)Cs(+) such a comparison was not possible because through-diffusion data are not available. Because through-diffusion methods cannot be applied to strongly sorbing tracers in reasonable time periods, in-diffusion combined with high-resolution abrasive peeling offers an excellent alternative for measuring the diffusion properties of strongly sorbing tracers in dense argillaceous rocks.

Diffusion of HTO, 36Cl- and 125I- in Opalinus Clay samples from Mont Terri. Effect of confining pressure.

Diffusion coefficients (T=23 +/- 2 degrees C) and accessible porosities for HTO, 36Cl(-) and 125I(-) were measured on Opalinus Clay (OPA) samples from the Mont Terri Underground Rock Laboratory (URL) using the through-diffusion technique. The direction of transport (diffusion) was perpendicular to bedding. Special cells that allowed the application of confining pressure were designed and constructed. The pressures ranged from 1 to 5 MPa, the latter value simulating the overburden at the Mont Terri URL (about 200 m). The test solution used in the experiments was a synthetic version of the Opalinus Clay pore water, which has Na(+) and Cl(-) as the main components (I=0.42 M). The measured values of the effective diffusion coefficients (D(e)) and rock capacity factors (alpha) are: D(e)=1.2-1.5 x 10(-11) m(2) s(-1) and alpha=0.09-0.11 for HTO, D(e)=4.0-5.5 x 10(-12) m(2) s(-1) and alpha=0.05 for 36Cl(-) and D(e)=3.2-4.6 x 10(-12) m(2) s(-1) and alpha=0.07-0.10 for 125I(-). For non-sorbing tracers (HTO, 36Cl) the rock capacity factor alpha is equal to the diffusion-accessible porosity epsilon. The experimental results showed that pressure only had a small effect on the value of the diffusion coefficients. Increasing the pressure from 1 to 5 MPa resulted in a decrease of the diffusion coefficient of approximately 17% for HTO, approximately 28% for 36Cl(-) and approximately 30% for 125I(-). Moreover, the diffusion coefficients for 36Cl(-) and 125I(-) are smaller than for HTO, which is consistent with an effect arising from anion exclusion. The diffusion coefficients of HTO and 125I(-) measured in this study are in good agreement with recent measurements at three other laboratories performed within the framework of a laboratory comparison exercise. The values of the diffusion-accessible porosities show a larger degree of scatter.

Chemical speciation and bioavailability of elements in the environment and their relevance to radioecology.

The commonly used terms 'chemical speciation' and 'bioavailability' are discussed and an attempt made to produce both qualitative and quantitative descriptions of their influence on the transfer of elements in the environment. The importance of considering the presence of the many different species of radionuclides which may occur in the environment is emphasized. The limitations of using concentration ratios, which take no account of the differing bioavailability of various chemical species of radionuclides, are discussed.

The uptake of TcO-4 by plants: a mathematical description.

A model describing the uptake of TcO-4 by spinach plants was developed. The equation relates both plant and soil parameters (e.g., growth, metabolism, concentration of TcO-4 and composition of the growth medium) to the concentration of Tc in the shoot of the plant. As the soil solution is the medium from which plants obtain nutrients and non-nutrients, the modeling parameters have been obtained from uptake experiments using nutrient solutions (= simulated soil solutions) as the growth medium. Two important model assumptions are: 1) that an equilibrium exists between TcO-4 in the plant and the growth medium and 2) that the leaf TcO-4 metabolism is a pseudofirst order reaction occurring in a non-constant volume.