Luc R. Van Loon

In-situ diffusion of HTO, 22Na+, Cs+ and I- in Opalinus Clay at the Mont Terri underground rock laboratory

Summary The diffusion properties of the Opalinus Clay were studied in the underground research laboratory at Mont Terri (Canton Jura, Switzerland) and the results were compared with diffusion data measured in the laboratory on small-scale samples. The diffusion of HTO, 22Na+, Cs+ and I- were investigated for a period of 10 months. The diffusion equipment used in the field experiment was designed in such a way that a solution of tracers was circulated through a sintered metal screen placed at the end of a borehole drilled in the formation. The concentration decrease caused by the diffusion of tracers into the rock could be followed with time and allowed first estimations of the effective diffusion coefficient. After 10 months, the diffusion zone was overcored and the tracer profiles measured. From these profiles, effective diffusion coefficients and rock capacity factors could be extracted by applying a two-dimensional transport model including diffusion and sorption. The simulations were done with the reactive transport code CRUNCH. In addition, results obtained from through-diffusion experiments on small-sized samples with HTO, 36Cl- and 22Na+ are presented and compared with the in situ data. In all cases, excellent agreement between the two data sets exists. Results for Cs+ indicated five times higher diffusion rates relative to HTO. Corresponding laboratory diffusion measurements are still lacking. However, our Cs+ data are in qualitative agreement with through-diffusion data for Callovo–Oxfordian argillite rock samples, which also indicate significantly higher effective diffusivities for Cs+ relative to HTO.

Trace metal–humate interactions. I. Experimental determination of conditional stability constants

The enhancement of mobility of radionuclides in the geosphere through complexation by humic substances is a source of uncertainty in performance assessment of radioactive waste repositories. Only very few data sets are available which are relevant for performance assessment of an underground repository for radioactive waste. Using the equilibrium dialysis-ligand exchange method developed at the Paul Scherrer Institut, conditional stability constants for the formation of complexes of Aldrich humic acid with Ca2+, NpO2+, Co2+, Ni2+, UO22+ and Eu3+ and complexes of Laurentian soil- and Suwannee River fulvic acid with Co2+, UO22+ and Eu3+ were measured. pH was varied between 5 and 10 and ionic strength between 0.02 and 0.2 M. The data are presented as equilibrium coefficients that are free from any model assumptions. The equilibrium coefficients increased in the order Ca2+≅NpO2+<Co2+< Ni2+<UO22+< Eu3+. The quality of the data is assessed in an extended discussion of statistical and systematical errors, and by a critical ‘rereview’ of the auxiliary stability constants used for the calculation of the equilibrium coefficients. An approximate overall uncertainty of 0.5 log-units is estimated for the stability data reported. The conditional stability constants were found to increase markedly with increasing pH in the case of Co2+, UO22+ and Eu3+. For Ni2+, Ca2+ and NpO2+ this effect was less pronounced. For all metal ions tested, the influence of ionic strength was of less importance, and the conditional stability constants did not show a significant dependence on the type of humic substances investigated.

Complexation of Th(IV) and Eu(III) by α-isosaccharinic acid under alkaline conditions

The complexation of Th(IV) and Eu(III) by α-isosaccharinic acid (ISA) has been studied in the pH range from 10.7 to 13.3 by batch sorption experiments, and the influence of Ca on the complexation was investigated. Sixteen data sets – each determined at variable ISA concentrations – are used to determine the stoichiometry of the complexation reactions and the stability constants. Based on best-fit analysis of the sorption data, it is postulated that 1:1 Th:ISA complexes are formed in the absence of Ca according to the complexation reaction: Th+ISA↔(ThISA)-4H+4H with log K=-10.1 at I=0.3 M. In the presence of Ca, the sorption data can be interpreted best by a mixed-metal complex, according to the complexation reaction: Th+2ISA+Ca↔(Th(ISA)2Ca)-4H+4H with logKCa=-3.6 at I=0.3 M. There are no indications that Ca participates in complexes of ISA with Eu. The sorption data suggest that 1:1 Eu:ISA complexes are dominant in the pH range from 10.7 to 13.3 according to the complexation reaction: Eu+ISA↔(EuISA)-4H+4H with logK=-30.6 at I = 0.3 M. It is important to note that the stoichiometric numbers and stability constants proposed here are not independent of the hydrolysis reactions of the two metal cations. Thus, the same hydrolysis data as used here have to be applied in speciation calculations with the ISA complexation data for Eu(III) and Th(IV).

Comparison between in situ and laboratory diffusion studies of HTO and halides in Opalinus Clay from the Mont terri

Summary A long-term single-borehole diffusion experiment (DI) using tritiated water (HTO) and stable iodide (127I-) was carried out In the Opalinus Clay of the Mont Terri Underground Rock Laboratory (URL). Diffusion coefficients DL and accessible porosity for HTO, 36Cl- and 125I- were also measured on centimetric Opalinus clay samples using the through diffusion technique. The evolution of tritium and iodide concentration in the injection system over time and in situ profiles were interpreted with a 3-D numerical simulation. A detailed analysis of the results pointed out the effect of a disturbed zone around the borehole with higher diffusion coefficients. The best estimate values for HTO and iodide in the undisturbed rock are DL = 5×10-11 m2/s and DL = 1.5×10-11 m2/s respectively. For the laboratory tests, DL values for HTO are in the range of 5×10-11 m2/s to 8.5×10-11 m2/s. For 125I- and 36Cl- the measured values are DL=νmber1.4×10-11 and DL=1.6×10-11 m2/s respectively. All HTO results obtained with a through diffusion technique are within the same range as those obtained in the in situ tests. The DL values obtained in diffusion cells with 125I- and 36Cl- and the value drawn from the interpretation of stable 127I- concentration profiles from the in situ tests are very close. In fact, some significant uncertainties could be identified (i.e. a likely chemical retention of iodide on argillites, effect of the disturbed zone).

TRACER DIFFUSION IN SINTERED STAINLESS STEEL FILTERS : MEASUREMENT OF EFFECTIVE DIFFUSION COEFFICIENTS AND IMPLICATIONS FOR DIFFUSION STUDIES WITH COMPACTED CLAYS

The use of porous filters is indispensable in laboratory- and field-scale diffusion studies, where sample confinement is needed for mechanical reasons. Examples are diffusion studies with compacted swelling clays or brittle clay stones. Knowledge of the diffusion properties of these filters is important in cases where they contribute significantly to the overall diffusive resistance in the experimental setup. In the present study, measurements of effective diffusion coefficients (Db) in porous, stainless steel filter discs are reported for tritiated H2O (HTO), 22Na+, Cs+, and Sr2+ before and after use of the filters in diffusion experiments with different clay minerals. The Db values for used filters were found to be less than those of the as-received filters by ∼30–50%. The Db values measured for the diffusion of HTO, 22Na+, Cs+, and Sr2+ in unused and used stainless steel filter discs correlated fairly well with the respective molecular diffusion coefficients in bulk water. Although such correlations are inherently associated with some uncertainties, they allow reasonable estimates to be made for diffusants for which no Db values are available. For the first time, a procedure is outlined that allows an integrative assessment to be made for the impact of the uncertainties in the filter diffusion properties on the combined standard uncertainties of the diffusion parameters obtained from through-diffusion experiments. This procedure can be used in the design and optimization of through-diffusion experiments in which the diffusive resistance of the porous filters must not be ignored. Shown here, as a general rule of thumb, is that, if the effective diffusion coefficient in the porous filter is at least three times larger than that in the clay, the choice of geometrical boundary conditions is rather uncritical, as long as the thickness of the clay sample is greater than that of the porous filters.

Translational diffusion of water and its dependence on temperature in charged and uncharged clays: A neutron scattering study

The water diffusion in four different, highly compacted clays [montmorillonite in the Na- and Ca-forms, illite in the Na- and Ca-forms, kaolinite, and pyrophyllite (bulk dry density rho(b)=1.85+/-0.05 gcm(3))] was studied at the atomic level by means of quasielastic neutron scattering. The experiments were performed on two time-of-flight spectrometers and at three different energy resolutions [FOCUS at SINQ, PSI (3.65 and 5.75 A), and TOFTOF at FRM II (10 A)] for reliable data analysis and at temperatures between 27 and 95 degrees C. Two different jump diffusion models were used to describe the translational motion. Both models describe the data equally well and give the following ranking of diffusion coefficients: Na-montmorillonite<or=Ca-montmorilloniteor=Na-montmorillonite>Ca-illite>Na-illite>or=kaolinite>pyrophyllite>or=water, in both jump diffusion models. For clays with a permanent layer charge (montmorillonite and illite) a reduction in the water content by a factor of 2 resulted in a decrease in the self-diffusion coefficients and an increase in the time between jumps as compared to the full saturation. The uncharged clay kaolinite exhibited no change in the water mobility between the two hydration states. The rotational relaxation time of water was affected by the charged clay surfaces, especially in the case of montmorillonite; the uncharged clays presented a waterlike behavior. The activation energies for translational diffusion were calculated from the Arrhenius law, which adequately describes the systems in the studied temperature range. Na- and Ca-montmorillonite (approximately 11-12 kJmol), Na-illite (approximately 13 kJmol), kaolinite and pyrophyllite (approximately 14 kJmol), and Ca-illite (approximately 15 kJmol) all had lower activation energies than bulk water (approximately 17 kJmol in this study). This may originate from the reduced number and strength of the H-bonds between water and the clay surfaces, or ions, as compared to those in bulk water. Our comparative study suggests that the compensating cations in swelling clays have only a minor effect on the water diffusion rates at these high densities, whereas these cations influence the water motion in non-swelling clays.

Seeming Steady-State Uphill Diffusion of 22Na+ in Compacted Montmorillonite

Whereas the transport of solutes in nonreactive porous media can mostly be described by diffusion driven by the concentration gradients in the external bulk water phase, the situation for dense clays and clay rocks has been less clear for a long time. The presence of fixed negative surface charges complicates the application of Ficks laws in the case of ionic species. Here we report the seeming uphill diffusion of a (22)Na(+) tracer in compacted sodium montmorillonite, that is, transport directed from a low to a high tracer concentration reservoir. In contrast to the classical through-diffusion technique the present experiments were carried out under the conditions of a gradient in the background electrolyte and using equal initial (22)Na(+) tracer concentrations on both sides of the clay sample. We conclude that the dominant driving force for diffusion is the concentration gradient of exchangeable cations in the nanopores. Commonly used diffusion models, based on concentration gradients in the external bulk water phase, may thus predict incorrect fluxes both in terms of magnitude and direction.

Consistent interpretation of the results of through-, out-diffusion and tracer profile analysis for trace anion diffusion in compacted montmorillonite.

Literature data for anion diffusion in compacted swelling clays contain systematic inconsistencies when the results of through-diffusion tests are compared with those of out-diffusion or tracer profile analysis. In the present work we investigated whether these inconsistencies can be explained by taking into account heterogeneities in the compacted samples; in particular increased porosities at the clay boundaries. Based on the combined results of out-diffusion, tracer profile analysis and the spatial distribution of the electrolyte anion in the clay, we conclude that the inconsistencies can indeed be resolved by taking into account a heterogeneous distribution of the total and the anion-accessible porosity. This, by definition, leads to a position dependence of the effective diffusion coefficient. Neglecting these effects results in a rather subordinate systematic error in the determination of effective diffusion coefficients of anions from through-diffusion tests with clay thicknesses in the centimetre range. However, stronger errors in terms of absolute values and conceptual interpretation may be introduced in out-diffusion tests and profile analyses of the diffused tracer. We recommend that anion diffusion tests should be accompanied by measurements of the total and anion-accessible porosity as a function of position in the direction of diffusion.

Importance of Interlayer Equivalent Pores for Anion Diffusion in Clay-Rich Sedimentary Rocks

The anion exclusion behavior in two different clay stones, Opalinus Clay (OPA) and Helvetic Marl (HM), was studied using a well-established experimental through-diffusion technique. The ionic strength of the pore water was varied between 0.01 and 5 M to evaluate its effect on the diffusion of HTO and 36Cl-. The total porosity determined by HTO-diffusion was independent of the ionic strength, while the anion accessible porosity varies with the ionic strength of the pore water. In the case of Opalinus Clay, the anion accessible porosity increases from 3% at low ionic strength (0.01 M) up to 8.4% at high ionic strength (5 M), whereas the anion accessible porosity of Helvetic Marl increases from 0.6% up to only 1.1%. The anion exclusion effect in HM is thus more pronounced than that in OPA, even at high ionic strength. This observation can be correlated to differences in mineralogy and to the fact that HM has a larger fraction of interlayer equivalent pores. Interlayer equivalent pores are small pores in compressed clay stones that are small enough to have, because of overlapping electric double layers, properties similar to those of interlayers and are therefore rather inaccessible for anions.

Dissolution–precipitation processes in tank experiments for testing numerical models for reactive transport calculations: Experiments and modelling

In the context of testing reactive transport codes and their underlying conceptual models, a simple 2D reactive transport experiment was developed. The aim was to use simple chemistry and design a reproducible and fast to conduct experiment, which is flexible enough to include several process couplings: advective-diffusive transport of solutes, effect of liquid phase density on advective transport, and kinetically controlled dissolution/precipitation reactions causing porosity changes. A small tank was filled with a reactive layer of strontium sulfate (SrSO4) of two different grain sizes, sandwiched between two layers of essentially non-reacting quartz sand (SiO2). A highly concentrated solution of barium chloride was injected to create an asymmetric flow field. Once the barium chloride reached the reactive layer, it forced the transformation of strontium sulfate into barium sulfate (BaSO4). Due to the higher molar volume of barium sulfate, its precipitation caused a decrease of porosity and lowered the permeability. Changes in the flow field were observed with help of dye tracer tests. The experiments were modelled using the reactive transport code OpenGeosys-GEM. Tests with non-reactive tracers performed prior to barium chloride injection, as well as the density-driven flow (due to the high concentration of barium chloride solution), could be well reproduced by the numerical model. To reproduce the mineral bulk transformation with time, two populations of strontium sulfate grains with different kinetic rates of dissolution were applied. However, a default porosity permeability relationship was unable to account for measured pressure changes. Post mortem analysis of the strontium sulfate reactive medium provided useful information on the chemical and structural changes occurring at the pore scale at the interface that were considered in our model to reproduce the pressure evolution with time.