Science & Technology Series n 334 (2008) Andra

23

European Bentonites as alternatives to MX-80

Dr. Dietrich Koch
S&B Industrial Minerals GmbH, Ruhrorter Strae 72, D-68219 Mannheim (Phone: 0049/621/80427-0, fax: 0621/80427-50, e-mail: d.koch@ikomineral s.com)

Abstract
For the management and disposal of radioactive waste, most of the European countries are working on solutions with bentonite as a key component. While over many years almost exclusively North American Wyoming bentonite, a natural sodium bentonite (MX-80 type), was tested as reference buffer material, since some years also different bentonites from European sources are examined and commercially available for this application. Bentonite has special characteristics, which make it very suitable for different environmental protection techniques. The possible future use of bentonite as sealing component in final repositories for radioactive waste is under investigation for two applications: (1) High grade bentonite as buffer material for embedment of the containers with radioactive waste, (2) Medium grade bentonite, possibly mixed with soil (e.g. crushed rock) or non swelling clays as backfill material for sealing the deposition tunnels. Differences in characteristics of Ca bentonite and Na bentonite are explained and recommendations are given for the use as buffer bentonite and as backfill material. The substantial characteristics of European bentonites are compared with those of MX-80 for the application as buffer bentonite. Information is given about high quality European bentonite mines and processing facilities. It is concluded by these recent research results that high grade Ca bentonite is equivalent with the so far preferred natural Na bentonite MX-80 for buffer application. The Milos Ca bentonite IBECO RWC is mentioned now as SKB reference bentonite. Keywords: bentonite, Ca bentonite, Na bentonite, buffer material, backfill material, disposal of radioactive waste

1. Introduction
Because of its unusual characteristics (2:1-layer nanosized structure of the montmorillonite mineral, cation exchange capacity, intracrystalline swelling) bentonite is used as a sealing component for different environmental protection techniques, (Koch, 2002). For the disposal of radioactive waste, most of the European countries are working on solutions with bentonite as a key component for buffer and backfill material. While over many years almost exclusively North American Wyoming bentonite, a natural sodium bentonite (MX-80 type), was analyzed as reference buffer material, since some years also different bentonites from European sources are examined for this application. Results so far confirm that there are alternatives to MX-80 for application as buffer (Pusch, 2001a, b) but also for backfilling. The main quality determining parameters of high-level radioactive waste (HLRW) bentonites are described in chapter 3.2.

2. Materials & methods

The bentonites described in this paper originate from Greece (island of Milos), Georgia (CIS), and the USA (Wyoming). The bentonite characteristics, as mentioned in this paper, were determined using methods listed in table 1.

3. Bentonite characteristics
Bentonite is the name for clay (weathered volcanic rock) which contains swellable 2:1 layer clay minerals of the smectite group, in particular the clay mineral montmorillonite as main component. The term smectite is used to describe a family of expansible 2:1 phyllosilicate minerals having permanent layer charge (between 0.2 and 0.6 charges per half unit cell) (Bailey, 1980) and the ability to embed and exchange inorganic and organic cations as well as liquids. The properties of bentonites

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Characteristic Cation exchange capacity (CEC) Chemical composition Density Mineralogical composition Montmorillonite content (Methylene-blue adsorption) pH value Swelling index Swelling pressure Water adsorption (Enslin/Neff-method) Water content Hydraulic conductivity Sulphur content Total organic content TOC

D. Koch
Unit mmol(eq)/kg wt.% g/cm wt.% wt.%
3

Method Cu-trien (Meier & Kahr, 1999) XRF Pusch (2002b), p. 144 XRD VDG P 69 pH meter

ml/2g kPa wt.% wt.% m/s wt.% wt.%

ASTM D 5890 Karnland et al. (2006), p. 35 DIN 18132 DIN 18121 (12 hrs, 105 C) DIN 18130 Thermogravimetric Analyzer Thermogravimetric Analyzer

Table 1: Bentonite characteristics and testing methods are based on the structure of smectites, mainly montmorillonite (Grim & Gven, 1978). Basic units of smectites are constructed of a single octahedral sheet sandwiched between two tetrahedral sheets sharing the apical oxygens of the tetrahedral sheets (Figure 1). Layer charge arises from substitutions in either the octahedral sheet (typically from the substitution of low charge species such as Mg2+, Fe2+, or Mn2+ for Al3+) or the tetrahedral sheet (where Al3+ or occasionally Fe3+ substitutes for Si4+), producing one negative charge for each substitution. This negative charge is distributed over the surface of the 2:1 layer platelets, while the edges and corners can bear some positive charges depending on the pH of the surrounding solution (Odom, 1984). The negative layer charges are neutralized by positively charged cations in the interlayer without entering the structural

Tetrahedral sheet Octahedral sheet

Tetrahedral sheet

Interlayer (Gallery)

exchangeable cations
neutral molecules (H2O)

Tetrahedral sheet

OH

Si,

Al, Fe, Mg

Figure 1: Basic units of smectite structure (Grim & Gven, 1978)

Science & Technology Series n 334 (2008) Andra 2:1 layers (Figure 2). In natural bentonites these can be predominantly Na+-ions (Wyoming bentonite, e.g. MX-80) or Ca2+-, Mg2+-ions (European bentonites). The interlayer (the space between the 2:1 layers) is hydrated and expansible. Therefore smectites are referred to as swelling clays (Lagaly, 1992). Bringing bentonite in contact with a surplus of water, e.g. by preparing an aqueous slurry, the dipole molecules of water are entering the interlayer area, accumulate to the positively charged cations and increase their hydration-shell. The effect is that the distance of the superimposed smectite particles is increasing (intracrystalline swelling). The characteristic properties of montmorillonite can be summarized in these three points: Structure of very small, thin, and flexible platelets with large surface Cation exchange capacity because of the negative charge of the elementary cell Capability of reversible adsorption of water in the interlayer space (intracrystalline swelling). 3.1. Differences in characteristics of Ca-bentonite and Na-bentonite In case of Ca bentonite, the electrical bonding forces between the Ca2+-ions und the negative charged particle surfaces are strong enough to preserve bundles of 15-20 2:1-layer platelets, building Ca montmorillonite quasi crystals. Therefore spatial conditions are limited for taking up additional water molecules.

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Ca bentonite can adsorb between 150% and 200% water related to its own weight. Contrary is the behaviour of Na bentonite. As the electrical interaction between the monovalent Na+-ions and the negatively charged platelets is much weaker compared to the Ca2+-ions with two positive charges, excess water molecules can enter completely the interlayer area, surrounding the Na+-ions with a larger hydration shell. The distances between the superimposed platelets are increased so much that the Na montmorillonite crystal bundles are disbanded into 15-20 single platelets each (see figures 3 and 5). One single 2:1 platelet has a thickness of ca. 1 nm (dehydrated). Its dimensions in length and width are in the range of 500-800 nm. The differences in swelling behaviour between Na- and Ca bentonite can be demonstrated by the swelling index (ASTM D 5890, figure 4) which is much larger for Na bentonite. Because of these differences in structure and properties, Na bentonite is preferred for most of the industrial and environmental applications. For most technical applications the European Ca bentonites are converted to Na bentonites by a technical ion-exchange process, called activation (Jasmund & Lagaly, 1993). Based on the patent of Prof. Endell (British Patent 4770, 1935), the soda-activation by an exchange of the Ca2+-ions by Na+-ions improves most of the properties of the basic Ca bentonites (Hofmann et al., 1933, 1934, see figure 5). [1]

soda-activation Ca2+ - Montmorillonite + Na2CO3 <2 Na+ - Montmorillonite + CaCO3 G de-activation

Figure 2: Model of Montmorillonite structure (Mller-Vonmoos, 1988)

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DRY
Calcium bentonite
2 2

D. Koch
IN SUSPENSION
d001: 1.5 nm hydrated cations limited swelling capacity d001: 2.0 nm

Ca2+ -ions hydration shell of 6 water molecules

+ Na2CO3 (soda activation) Sodium bentonite

hydrated cations

d 001:

=Na+ -ions

d 001: 1.2 nm high swelling capacity

hydration shell of 4 water molecules water molecules

Figure 3: Cation-exchange and swelling behaviour of Ca- and Na bentonites

Figure 4: Swelling index. Ca-bentonite (2 g) in water: 5 ml (left); Na-bentonite (2 g) in water: 32 ml (right).

On industrial scale, the natural Ca bentonite (with 28 % water content) is intensively mixed with an adequate amount of Na2CO3 that corresponds to the CEC. The Ca2+-ions react with the CO32--anions forming calcium carbonate of low solubility. According to this process, the Na+-ions can completely replace the Ca2+-ions as interlayer cations (Lagaly et al., 1981). The resulting activated Na bentonite can easily be dispersed in water, building up a colloidal dispersion. Because of their electrical charges on the surface and at the edges and corners, the dispersed platelets are building up voluminous structures like card houses or ribbons, depending on the pH value of the dispersion (see figure 5). These voluminous structures are responsible for the special rheological properties (e.g. thixotropy) of bentonite suspensions. Reaction (1) can run in reverse if a Na bentonite comes in contact with a surplus of free Ca2+-ions, e.g. by hard water with high content of Ca2+-ions. The polyvalent cations can (again) partly or totally replace the Na+-ions (de-activation) with the effect, that the montmorillonite platelets agglomerate to semicrystallites. During the technical use of bentonite suspensions, e.g. as drilling slurries, this de-activation of Na bentonite can be identified by (unwanted) flocculation effects and solid/liquid separations. In case of buffer application, the reaction of Na bentonite with saline rock water could result in structural changes like shrinking or cracking because of ion-exchange reactions. If the water adsorption can take place without spatial restrictions, Na bentonite has a clearly higher swelling

Science & Technology Series n 334 (2008) Andra

Grain-size % < 2 m ca. 20 ca. 80 Water adsorption (E.N. Value, %) 150 - 200 500 - 700

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Bentonite type Ca bentonite Na bentonite

Swelling volume (ml) 5-8 25 - 35

pH-Value 7.5 - 8 9.5 - 10.5

Table 2: Comparison of properties of typical Na and Ca bentonites volume than Ca bentonite (Figure 4). Upon loading, the swelling pressure depends on the density of the bentonite, the salinity of the pore water, and the major type of interlayer cation (Lagaly, 2006). Therefore Na bentonite like MX-80 was preferred as a standard buffer material for a long time. Under spatially limited conditions without free swelling, e.g. after compaction, bentonite can develop rather high swelling pressures. The space between the montmorillonite platelets is smaller and the repulsion between the negatively charged surfaces is greater (Pusch, 2006). The difference in swelling pressure between Na bentonite and Ca bentonite becomes negligible at densities lager than about 1900 kg/m , when the stacks of lamellae have been forced together so much that the microstructural patterns are similar (Pusch, 2002a, p. 130). 3.2. Na bentonite or Ca bentonite as buffer? The Wyoming type bentonite MX-80 was analyzed for more than 20 years by all institutes that were concerned with this topic, as reference bentonite for the buffer application. In 2001 in a meeting of the author with Roland Push and the Swedish Nuclear Fuel and Waste Management Co (SKB), the long-term stability of HLRW bentonite in a saline environment was discussed. The possibilities of ion-exchange of Na bentonite by groundwater containing Ca2+/Mg2+-ions and as consequence possible structural changes like shrinking or cracking were discussed. Therefore the author made the proposal for examination of Ca bentonite as less sensitive alternative for host rock formations with saline rock water. After several years of analyzing, the principle suitability of high grade Ca bentonite (montmorillonite content > 75 wt.%) as

Figure 5: Soda-activation and de-activation by ion-exchange

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D. Koch Mechanical stability (low dispersibility) against flowing rock water (Kaufhold & Dohrmann, 2008) Chemical stability against electrolyte rich rock water. For backfill there are different options for the filling material as well as for the construction technique of backfill operation (Pusch, 2002b). As backfilling material either a high grade bentonite can be blended with inert fillers (crushed rock, sand, or non swelling clay) or a medium grade bentonite (with a montmorillonite content between 50 and 65 wt.%) could be used, if available in constant quality and sufficient quantity. For backfill we give the same recommendation for a suitable bentonite type as for buffer. Depending on the host rock formation, non-activated Ca bentonite should be used, when electrolyte-rich rock water can come into contact with the backfill, while Na bentonite can be used in environment without any saline load. For a medium grade bentonite as backfill material, we recommend to specify as the main quality determining parameters: Medium montmorillonite content (e.g. 50-65 wt.%) Medium cation exchange capacity (e.g. 0.55-0.70 mmol(eq)/g) Medium water adsorption (e.g. 150-200% Enslin/Neff value) Low hydraulic conductivity (e.g. Kf = 10-10-10-13 m/s) and additionally for repositories in hard rock formation with saline rock water environment: Mechanical stability (low dispersibility) against flowing rock water and upward movement of the buffer bentonite (Kaufhold & Dohrmann, 2008) Chemical stability against electrolyte rich rock water.

buffer material was confirmed by SKB (Sellin et al., 2005). The substantial influence of electrolyte concentration in pore water on Na and Ca bentonite has been described by Pusch (2006). In the meantime S&Bs calcium dominated Milos bentonite IBECO RWC is listed as SKB reference buffer material, as well as the Wyoming bentonite MX-80. In table 4 the chemical and mineralogical composition and some physical properties of bentonites are summarized, which had been tested as alternatives to MX-80 as buffer bentonite. Besides the Ca bentonite IBECO RWC also as another natural Na bentonite IBECO RWN was analyzed. From our experience as bentonite producer, the question for the most suitable bentonite type as buffer can be answered in such a way that for hard rock formations with saline rock water environment Ca bentonite should be preferred. For repositories in a clay stone as host rock formation, where no saline water is to be expected, a Na bentonite can be used. In order to achieve a long-term stability under final repository conditions we recommend to specify the following main quality determining parameters of HLRW bentonites for buffer application: High montmorillonite content (e.g. 75-90 wt.%) High cation exchange capacity (e.g. 0.80-0.95 mmol(eq)/g) Medium water adsorption (e.g. 150-200% Enslin/Neff value) Low hydraulic conductivity (e.g. Kf = 10-11-10-14 m/s) Low sulphur content (still to specify) Low organic matter content (still to specify) and additionally for repositories in hard rock formation with saline rock water environment:

Density & saturation MX-80 IBECO, Na IBECO, Ca RMN Beidellite Saponite Kunigel Friedland

1300 0.06 -

1500 0.2 -

1700 0.4 0.45 -

1800 0.8-0.9 0.6-1 0.2 1.9* 1.5 2.5 0.2 0.1

1900 1.4 2.5** 0.3

2000 4-5 4-5 5 3.9** 4.2 8.8 0.9 0.8-1

2100 10-12 2.2.5

0.05

* Density at saturation: 1850 kg/m3 ** Mixture with 5% graphite and 10% quartz powder- Density at saturation: 1950 kg/m3

Table 3: Comparison of swelling pressures of Na and Ca bentonites (Pusch, 2002a, p. 130)

Science & Technology Series n 334 (2008) Andra

IBECO RWC Origin Chemical Composition [XRF] SiO2 Al2O3 Fe2O3 TiO2 CaO MgO Na2O K2O LOI Smectite Illite/Mica Quartz Calcite Others CEC Swelling vol. Enslin-Neff [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] [wt.%] mmol(eq)/kg ml/2g % 55.2 16.5 5.6 0.7 7.4 3.1 0.5 0.5 9.7 75 85 <4 <4 8 12 <4 0.80 - 0.90 6 - 10 110 - 150 59.5 18.6 3.5 0.4 2.3 4.5 2.4 1.3 7.2 85 95 26 <4 35 <4 0.95 - 1.05 22 - 26 480 - 520 55.8 18.1 5.5 0.7 5.1 3.8 2.8 0.9 7.3 65 75 24 57 69 5 16 0.70 - 0.80 28 - 32 650 - 800 Greece Ca-bentonite IBECO RWN Georgia (CI S) Nat. Na-bentonite MX-80 Wyoming Nat. Na-bentonite

29

Mineralogy [XRD]

[Physical Properties]

Table 4: Characteristics of different buffer bentonites

4. Summary and conclusions

Recent research results (Karnland et al., 2006) confirmed the equivalence of high grade Ca bentonite with so far preferred natural Na bentonite (MX-80 type) for buffer application. The Milos Ca bentonite IBECO RWC is mentioned now also as SKB reference bentonite. Depending on the type of host rock, the presence of (saline) water, and the application as buffer or backfill bentonite, S&B Industrial Minerals recommends different types of bentonites (Table 5). S&B Industrial Minerals as the leading bentonite producer in Europe owns several bentonite mines and

production plants in Europe and outside of Europe, and can offer all grades of bentonite that can be used in the above mentioned buffer and backfill applications. Natural Na bentonite Technical activated Na bentonite Non-activated Ca bentonite. Figure 6 shows a part of the worldwide largest bentonite mine Angeria on the Greek island Milos. This mine is 2.5 km long, 600 m wide, 130 m deep, and has 27 mio tons current proven reserves in different qualities. The bentonite excavation is done by open pit mining.

Host rock Hard rock with saline water Hard rock with saline water Clay rock Clay rock Buffer Backll Buffer Backll

Application

Bentonite type High grade Ca bentonite Medium grade Ca bentonite High grade Na bentonite Medium grade Na bentonite

Table 5: Recommendations of bentonite types for different host rocks and different HLRW applications

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D. Koch

Figure 6: Milos, largest bentonite mine worldwide

References
Bailey S.W. (1980). Summary of recommendations of AIPEA nomenclature committee on clay minerals. American Mineralogist, 65, 1-7 British Patent 47 710 (12.06.1935), Ger. (16.06.1 934) Grim R. E. & Gven N. (1978). Bentonites, Geology, Mineralogy, Properties and Uses. Elsevier, Amsterdam Hofmann U., Endell K., Wilm D. (1933). Kristallstruktur und Quellung von Montmorillonit. (Das Tonmineral der Bentonittone). Z Kristallographie 86, 340-348 Hofmann U., Endell K., Wilm D. (1934). Rntgenographische und kolloidchemische Untersuchungen ber Ton. Angewandte Chemie, 47, 539-547 Jasmund K. & Lagaly G. (1993). Tonminerale und Tone. Steinkopff Verlag Darmstadt Kaufhold S. & Dohrmann R. (2008). Detachment of colloids from bentonites in water. Applied Clay Science, 39, 50-59. Karnland O., Olsson S. & Nilsson U. (2006). Mineralogy and sealing properties of various bentonites and smectite-rich clay materials. SKB Technical Report TR-06-30. Koch D. (2002). Bentonites as a basic material for technical base liners and site encapsulation cut-off walls. Applied Clay Science 21, 1-11. Lagaly G. (1992). From clay mineral crystals to clay mineral dispersions. In: Dobis B (ed) Coagulation and flocculation: theory and application. 427-494. Lagaly G. (2006). Colloid Clay Science. In: Bergaya F., Theng B.K.G. and Lagaly G. (ed) Handbook of Clay Science, Elsevier, 186-188. Lagaly G., Mller-Vonmoos M., Kahr G. & Fahn R. (1981). Vorgnge bei der Sodaaktivierung von Bentoniten am Beispiel eines Bentonits von Neuseeland. Keramische Z. 33, 278-283. Meier L.P, & Kahr G. (1999). Determination of the cation exchange capacity (CEC) of clay minerals using the complexes of copper (II) ion with triethylenetetraamine and tetraethylenepentamine. Clays and Clay Minerals 47, 386-388. Mller-Vonmoos M. (1988). Tonmineralogie und Bodenmechanik. Mitteilungen des Institutes fr Grundbau und Bodenmechanik Eidgenssische Hochschule Zrich, No. 133. Odom I.E. (1984). Smectite clay minerals: properties and uses. Phil Trans R Soc London A, 311-391. Pusch R. (2001a). Origin and exploitable amounts of Greek bentonites and comparison of one representative (IBECO-Seal M 90), with MX-80. Unpublished report. Pusch R. (2001b). Report on preparation of highly compacted blocks of IBECO-SEAL M 90 Clay material. Unpublished report. Pusch R. (2002a). The Buffer and Backfill Handbook. Part 2: Materials and techniques. SKB Technical Report TR-02-12. Pusch R. (2002b). The Buffer and Backfill Handbook. Part 1: Definitions, basic relationships and laboratory methods. SKB Technical Report TR-02-20. Pusch R. (2006). Mechanical properties of clays and clay minerals. In: Bergaya F, Theng BKG and Lagaly G (ed), Handbook of Clay Science, Elsevier, 250-251. Sellin P., Karnland O., Nilsson U. & Olsson S. (2005). Experimental study of sealing properties of commercial bentonites related to bentonite mineralogy and water solution composition. In: conference abstracts of ANDRA 2nd International meeting, March 14-18 2005 in Tours, Clays in Natural & Engineered Barriers for Radioactive Waste Confinement, page 229 VDG Merkblatt P 69, (1988) Prfung von Bindetonen p. 5