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Pore Geometry as a Limiting Factor for Anion Diffusion in Argillaceous Rocks

Published online by Cambridge University Press:  01 January 2024

C. Wigger ,
M. Plöze  and
L. R. Van Loon
C. Wigger*
Affiliation:
Laboratory for Waste Management, Paul Scherrer Institut, 5232, Villigen PSI, Switzerland
M. Plöze
Affiliation:
Institute for Geotechnical Engineering, 8093, Zurich, Switzerland
L. R. Van Loon
Affiliation:
Laboratory for Waste Management, Paul Scherrer Institut, 5232, Villigen PSI, Switzerland
*
*E-mail address of corresponding author: cornelia.wigger@psi.ch
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Abstract

Several barrier types are envisaged to minimize the release of radionuclides from waste matrices into groundwater. In a number of countries argillaceous rocks make up the natural barrier that will isolate radioactive substances from the aquifer. The present study addresses the influence of pore geometry as a limiting factor for anion diffusion in argillaceous rocks. Irrespective of the pore core size, anion diffusion can be limited by the pore-size opening, i.e. if the pore opening is so narrow that the electric double layers overlap and form a barrier to anions irrespective of the pore size. This so-called ‘bottleneck effect’ limits the anion diffusion. The present study extends previous investigations that focused on other factors which limit anion diffusion, e.g. mineralogy or interlayer equivalent pores. The existence of bottleneck pores was confirmed by effective tortuosity calculations and retention-potential measurements using mercury intrusion porosimetry. On the basis of two different core samples from argillaceous rocks from Switzerland, Opalinus Clay and Helvetic Marl, this work shows evidence of the existence of bottleneck pores. The larger permanent anion exclusion in the Helvetic Marl sample compared to the Opalinus Clay sample can be explained by the larger retention potential and larger effective tortuosity of the Helvetic Marl rock, which indicates more pores with bottleneck effects than is the case for the Opalinus Clay rock.

Keywords

Bottleneck EffectOpalinus ClayPorosityRetention PotentialTortuosity
Type
Article
Information
Clays and Clay Minerals , Volume 66 , Issue 4 , August 2018 , pp. 329 - 338
Copyright
Copyright © Clay Minerals Society 2018

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References

Altmann, S. (2008) Geochemical research: A key building block for nuclear waste disposal safety cases. Journal of Contaminant Hydrology, 102, 174–179.CrossRefGoogle ScholarPubMed
Appelt, H., Holtzclaw, K., and Pratt, P. (1975) Effect of anion exclusion on the movement of chloride through soils. Soil Science Society of America Journal, 39, 264–267.CrossRefGoogle Scholar
Baeyens, B. and Bradbury, M. H. (2004) Cation exchange capacity measurements on illite using the sodium and cesium isotope dilution technique: effects of the index cation, electrolyte concentration and competition: modeling. Clays and Clay Minerals, 52, 421–431.CrossRefGoogle Scholar
Bolt, G.H. and de Haan, F.A.M. (1979) Anion exclusion in soil. Pp. 233–257 in: Soil Chemistry: B. Physico-Chemical Models (Bolt, G.H., editor). Developments in Soil Science, Vol. 5B, Elsevier, Amsterdam.CrossRefGoogle Scholar
Chagneau, A.L., Tournassat, C., Steefel, C.I., Bourg, I.C., Gaboreau, S.P., Esteve, I.N., Kupcik, T., Claret, F., and Schafer, T. (2015) Complete restriction of 36Cl– diffusion by celestite precipitation in densely compacted illite. Environmental Science & Technology Letters, 2, 139–143.CrossRefGoogle Scholar
Choi, J.-W. and Oscarson, D. (1996) Diffusive transport through compacted Na-and Ca-bentonite. Journal of Contaminant Hydrology, 22, 189–202.CrossRefGoogle Scholar
Descostes, M., Blin, V., Bazer-Bachi, F., Meier, P., Grenut, B., Radwan, J., Schlegel, M.L., Buschaert, S., Coelho, D., and Tevissen, E. (2008) Diffusion of anionic species in Callovo-Oxfordian argillites and Oxfordian limestones (Meuse/Haute–Marne, France). Applied Geochemistry, 23, 655–677.CrossRefGoogle Scholar
Diamond, S. (1970) Pore size distributions in clays. Clays and Clay Minerals, 18, 7–23.CrossRefGoogle Scholar
Flury, M. and Gimmi, T. F. (2002) Section 6.2 Solute diffusion. In: Miscible solute transport. Pp. 1353–1351 in: Methods of Soil Analysis, 4, Soil Science Society of America, Madison, Wisconsin, USA.Google Scholar
Gaboreau, S., Robinet, J.C., and Prêt, D. (2016) Optimization of pore-network characterization of a compacted clay material by TEM and FIB/SEM imaging. Microporous and Mesoporous Materials, 224, 116–128.CrossRefGoogle Scholar
Giesche, H. (2006) Mercury porosimetry: a general (practical) overview. Particle & Particle Systems Characterization, 23, 9–19.CrossRefGoogle Scholar
Gimmi, T. and Fernández, A.M. (2017) Physical characterisation of pores and pore water of samples from the Schlattingen borehole. Technical Report NAB 16-71. Nagra, Wettingen, Switzerland.Google Scholar
Grambow, B. (2008) Mobile fission and activation products in nuclear waste disposal. Journal of Contaminant Hydrology, 102, 180–186.CrossRefGoogle ScholarPubMed
Harvey, K.B. (1996) Measurement of Diffusive Properties of Intact Rock. Atomic Energy of Canada Ltd.Google Scholar
Hemes, S., Desbois, G., Urai, J.L., Schröppel, B., and Schwarz, J.-O. (2015) Multi-scale characterization of porosity in Boom Clay (HADES-level, Mol, Belgium) using a combination of X-ray μ-CT, 2D BIB-SEM and FIB-SEM tomography. Microporous and Mesoporous Materials, 208, 1 –20.CrossRefGoogle Scholar
Houben, M., Desbois, G., and Urai, J.L. (2013) Pore morphology and distribution in the shaly facies of Opalinus Clay (Mont Terri, Switzerland): Insights from representative 2D BIB-SEM investigations on mm to nm scale. Applied Clay Science, 71, 82–97.CrossRefGoogle Scholar
Katsube, T., Melnyk, T., and Hume, J. (1986) Pore structure from diffusion in granitic rocks, Atomic Energy of Canada Limited, Whiteshell Nuclear Research Establishment.Google Scholar
Kestin, J., Khalifa, H.E., and Correia, R.J. (1981) Tables of the dynamic and kinematic viscosity of aqueous NaCl solutions in the temperature range 20–150°C and the pressure range 0.1–35 MPa. Journal of Physical and Chemical Reference Data, 10, 71–88.CrossRefGoogle Scholar
Matusewicz, M., Pirkkalainen, K., Liljeström, V., Suuronen, J.P., Root, A., Muurinen, A., Serimaa, R., and Olin, M. (2013) Microstructural investigation of calcium montmorillonite. Clay Minerals, 48, 267–276.CrossRefGoogle Scholar
Mazurek, M., Waber, N., Mäder, U., Gimmi, T., de Haller, A., and Koroleva, M. (2012) Geochemical synthesis for the Effingen Member in boreholes at Oftringen, Gösgen and Küttigen. Technical Report NTB 12-07. Nagra, Wettingen, Switzerland.Google Scholar
Melnyk, T. and Skeet, A. (1986) An improved technique for the determination of rock porosity. Canadian Journal of Earth Sciences, 23, 1068–1074.CrossRefGoogle Scholar
Moors, H. (2005) Topical report on the effect of the ionic strength on the diffusion accessible porosity of Boom Clay. SCK CEN, Mol, Belgium, report SCK CEN-ER-02.Google Scholar
Moro, F. and Böhni, H. (2002) Ink-bottle effect in mercury intrusion porosimetry of cement-based materials. Journal of Colloid and Interface Science, 246, 135–149.CrossRefGoogle ScholarPubMed
Muurinen, A. (1994) Diffusion of anions and cations in compacted sodium bentonite. VTT Publications 168, Technical Research Centre of Finland, Espoo, Finland.Google Scholar
Schmatz, J., Vrolijk, P., and Urai, J. (2010) Clay smear in normal fault zones–The effect of multilayers and clay cementation in water-saturated model experiments. Journal of Structural Geology, 32, 1834–1849.CrossRefGoogle Scholar
Smith, D., Pivonka, P., Jungnickel, C., and Fityus, S. (2004) Theoretical analysis of anion exclusion and diffusive transport through platy-clay soils. Transport in Porous Media, 57, 251–277.CrossRefGoogle Scholar
Song, Y., Davy, C.A., Bertier, P., and Troadec, D. (2016) Understanding fluid transport through claystones from their 3D nanoscopic pore network. Microporous and Mesoporous Materials, 228, 64–85.CrossRefGoogle Scholar
Tevissen, E., Soler, J., Montarnal, P., Gautschi, A., and Van Loon, L.R. (2004) Comparison between in situ and laboratory diffusion studies of HTO and halides in Opalinus Clay from the Mont Terri. Radiochimica Acta/International Journal for Chemical Aspects of Nuclear Science and Technology, 92, 781–786.Google Scholar
Thompson, M.L., McBride, J.F., and Horton, R. (1985) Effects of drying treatments on porosity of soil materials. Soil Science Society of America Journal, 49, 1360–1364.CrossRefGoogle Scholar
Tournassat, C. and Appelo, C.A.J. (2011) Modelling approaches for anion-exclusion in compacted Na-bentonite. Geochimica et Cosmochimica Acta, 75, 3698–3710.CrossRefGoogle Scholar
Tournassat, C., Bourg, I.C., Holmboe, M., Sposito, G., and Steefel, C.I. (2016a) Molecular dynamics simulations of anion exclusion in clay interlayer nanopores. Clays and Clay Minerals, 64, 374–388.CrossRefGoogle Scholar
Tournassat, C., Gaboreau, S., Robinet, J.-C., Bourg, I.C., and Steefel, C.I. (2016b) Impact of microstructure on anion exclusion in compacted clay media. Pp. 137–149 in: Filling the Gaps–From Microscopic Pore Structures to Transport Properties in Shales (Schäfer, T., Dohrmann, R., and Greenwell, H.C., editors). Workshop Lectures Series, 21. The Clay Minerals Society, Chantilly, Virginia, USA.CrossRefGoogle Scholar
Van Brakel, J. and Heertjes, P.M. (1974) Analysis of diffusion in macroporous media in terms of a porosity, a tortuosity and a constrictivity factor. International Journal of Heat and Mass Transfer, 17, 1093–1103.CrossRefGoogle Scholar
Van Loon, L.R. and Soler, J.M. (2004) Diffusion of HTO, 36CI–, 125i– and 22Na+ in Opalinus Clay: Effect of Confining Pressure, Sample Orientation, Sample Depth and Temperature. Nagra Technischer Bericht NTB 03-07. Paul-Scherrer-Institut, PSI. Nagra, Wettingen, Switzerland.Google Scholar
Van Loon, L.R., Glaus, M.A., and Müller, W. (2007) Anion exclusion effects in compacted bentonites: Towards a better understanding of anion diffusion. Applied Geochemistry, 22, 2536–2552.CrossRefGoogle Scholar
Vilks, P. and Miller, N. (2007) Evaluation of experimental protocols for characterizing diffusion in sedimentary rocks. Nuclear Waste Management Organization Report TR-2007-11. Nuclear Waste Management Organization, Toronto, Canada.Google Scholar
Vrolijk, P.J., Urai, J.L., and Kettermann, M. (2016) Clay smear: Review of mechanisms and applications. Journal of Structural Geology, 86, 95–152.CrossRefGoogle Scholar
Wardlaw, N. and Cassan, J. (1979) Oil recovery efficiency and the rock-pore properties of some sandstone reservoirs. Bulletin of Canadian Petroleum Geology, 27, 117–138.Google Scholar
Wardlaw, N. and McKellar, M. (1981) Mercury porosimetry and the interpretation of pore geometry in sedimentary rocks and artificial models. Powder Technology, 29, 127–143.CrossRefGoogle Scholar
Washburn, E.W. (1921a) The dynamics of capillary flow. Physical Review, 17, 273.CrossRefGoogle Scholar
Washburn, E.W. (1921b) Note on a method of determining the distribution of pore sizes in a porous material. Proceedings of the National Academy of Sciences, 7, 115–116.CrossRefGoogle Scholar
Wigger, C. and Van Loon, L.R. (2017) Importance of interlayer equivalent pores for anion diffusion in clay-rich sedimentary rocks. Environmental Science & Technology, 51, 1998–2006.CrossRefGoogle ScholarPubMed
Wigger, C., Gimmi, T., Muller, A.C.A., and Van Loon, L.R. (2018) The influence of small pores on the anion transport properties of natural argillaceous rocks–a pore size distribution investigation of Opalinus Clay and Helvetic Marl. Applied Clay Science, 156, 134–143.CrossRefGoogle Scholar