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Clay Mineralogy of the Boda Claystone Formation (Mecsek Mts., SW Hungary)

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Clay Mineralogy of the Boda Claystone Formation (Mecsek Mts., SW Hungary) Open Geosci. 2016; 8:259–274 Research Article Open Access Tibor Németh*, Zoltán Máthé, Péter Pekker, István Dódony, Viktória Kovács-Kis, Péter Sipos, Ildikó Cora, and Ivett Kovács Clay mineralogy of the Boda Claystone Formation (Mecsek Mts., SW Hungary) DOI 10.1515/geo-2016-0024 1 Introduction Received March 06, 2014; accepted August 28, 2015 Abstract: Boda Claystone Formation (BCF) is the host rock Investigations on Boda Claystone Formation (abbreviated of the planned site for high level nuclear waste repository in the following as BCF) as a potential rock formation for in Hungary. Samples representing the dominant rock types high level nuclear waste (HLW) disposal began in 1989 of BCF were studied: albitic claystone, claystone with high and goes on up to present in several research stage in illite content, and analcime bearing claystone. Clay min- the ’90s and 2000s. During the rst years, research was erals in these three rock types were characterized by X- supported by Paks Nuclear Power Plant. Since 1998 Pub- ray powder diraction (XRD), transmission electron mi- lic Limited Company for Radioactive Waste Management croscopy (TEM) and thermal analysis (DTA-TG), and the (PURAM) as a Hungarian governmental agency has the re- results were discussed from the point of view of the ra- sponsibility and nancial funds for the coordination of dionuclide sorption properties being studied in the future. the studies. PURAM considers BCF as suitable rock for- Mineral compositions of bulk BCF samples vary in wide mation for HLW since 1999. Favourable properties which ranges. In the albitic sample, besides the dominant illite, support the suitability of BCF based on the studies [1–4] few percent of chlorite represents the layer silicates in the are the followings: BCF is a massive, homogeneous rock clay fraction. Illite is the dominating phase in the illitic body with signicant extension and thickness (700-900 sample, with a few percent of chlorite. HRTEM study re- m); it has low bulk-porosity (0.6-1.4%) and very low perme- −11 −13 vealed that the thickness of illite particles rarely reaches ability 10 -10 m/s, referring to diusion-dominating 10 layers, usually are of 5-6 TOT layer thick. Illite crystals transport conditions; the hydrogeological and ow system are generally thicker in the albitic sample than in the il- has long term stability; high proportion of clay minerals litic one. The signicant dierence between the clay min- and analcime provide good adsorptive properties; it has eral characterisitics of the analcimous and the other two favourable geotechnical features due to the subordinate samples is that the former contains regularly interstrati- amount of swelling clays and high amount of albite. Disad- ed chlorite/smectite beside the dominant illite. vantage is the presence of abandoned tunnels and cavities Based on the structural and chemical data two illite type of a closed uranium mine. minerals are present in the BCF samples: 1M polytype con- Physical and chemical properties of clay minerals, taining octahedral Fe and Mg besides Al, 2M polytype il- such as sorption, sealing and isolation capacity are im- lite generally is free of Fe and Mg. Close association of very portant from the point of view of radionuclide migration thin illite plates and nanosized hematite crystals is typical in rocks. All of these properties are function of the crystal textural feature for BCF. chemical and structural, as well as textural features of clay The goal of this study is to provide solid mineralogical ba- sis for further studies focusing on radionuclide sorption Zoltán Máthé: properties. Mecsekérc Plc., H-7614, Pécs, Hungary Péter Pekker, Ildikó Cora: Hungarian Academy of Sciences - Uni- Keywords: illite polytypes; HRTEM; nuclear waste reposi- versity of Miskolc, Materials Science Research Group, Miskolc, Hun- tory; analcime; hematite gary István Dódony: Department of Mineralogy, Eötvös University, Bu- dapest Viktória Kovács-Kis: Hungarian Academy of Sciences, Institute for *Corresponding Author: Tibor Németh: Hungarian Academy Technical Physics and Materials Science, Thin Film Physics Group, of Sciences, Institute for Geological and Geochemical Research, Budapest, H-1121, Hungary Budapest, H-1112, Hungary, E-mail: [email protected] Péter Sipos, Ivett Kovács: Hungarian Academy of Sciences, Insti- *Corresponding Author: Tibor Németh: Department of Mineral- tute for Geological and Geochemical Research, Budapest, H-1112, ogy, Eötvös University, Budapest Hungary © 2016 T. Németh et al., published by De Gruyter Open. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License. The article is published with open access at www.degruyter.com. 260 Ë T. Németh et al. minerals. Therefore, characterization of clay minerals in greenish-gray claystone, siltstone) can be observed in its details is crucial in the evaluation of the technical proper- lower and upper transitional zones (Figure 2). ties of a given rock formation. Despite the extensive study The BCF deposited in a shallow-water salt lake envi- of BCF since two decades, till now, there is no any work ronment surrounded by dry to saline mudat, under semi- studying its clay mineralogy from this aspect. Our goal is to arid to arid climatic conditions [7–9, 11]. give a detailed mineralogical characterization of the most typical BCF samples, in order to provide a mineralogical basis for the radionuclide sorption studies. Moreover, the 2.2 Mineralogy and petrology results are discussed from the point of view of presumable radionuclide sorption properties of the claystone. The main rock-forming minerals of the BCF in the pe- rianticlinal structure (WMA) are clay minerals (domi- nantly illite-muscovite and chlorite, associated with mi- 2 The Boda Claystone Formation nor; smectite, kaolinite, vermiculite), authigenic albite, detrital quartz, carbonate minerals (calcite, dolomite) and hematite [2, 8, 9, 12]. In addition, some barite, an- 2.1 Geologic setting hydrite, authigenic K-feldspar and detrital constituents (muscovite, biotite, chlorite, zircon, rutile, apatite, il- The following paragraphs summarize the knowledge on menite, Ca-bearing plagioclase) were always also identi- the geological setting, petrology and mineralogy of BCF ac- ed in trace amounts. The authigenic albite is present as cumulated hitherto. albite cement (typical for all rock types of BCF), and few The sedimentary sequence of the Upper Permian Boda millimetre sized irregular vesicles lled with albite and Claystone Formation is located in Western Mecsek Moun- carbonate minerals (typical for albitic claystone), and al- tains, southern Transdanubia, SW Hungary (Figure 1). The bite replacement of detrital feldspars in sandstone beds Mecsek Mts. is part of the Tisza Megaunit comprising [2, 8, 12]. Carbonate minerals (ne-grained and sparry cal- the basement of the south-eastern half of the Pannonian cite and euhedral rhombohedral dolomite) and authigenic Basin. The continental sedimentation in the Mecsek Mts. K-feldspar are always present in these vesicles. Electron began in the Early Permian (Korpád Sandstone Formation) microprobe analyses of these pore-lining carbonates show and terminated in the Lower Triassic [5]. The BCF is part of that they always contain Mn and Fe (Mn > Fe). On the ba- this about 2000-4000 m thick siliciclastic sequence (conti- sis of their morphology these albite-, carbonate- and K- nental red beds). On the basis of data from boreholes and feldspar-lined vesicles are interpreted as replacement of geological mappings the extension of BCF is around 150 the previous halite crystals ("hopper halite") [11]. 2 2 km , and only 15 km area outcrop exposed at the Boda vil- The BCF recovered by borehole Ib-4 (Gorica block) dif- lage region in W Mecsek Mts. (Figure 1). Two occurrences of fers in its mineralogical composition. The BCF at Gorica BCF are known: 1. perianticlinal structure of the W Mecsek block contains abundant analcime in addition to above Mts (WMA); 2. so called Gorica block. In the Gorica block listed minerals [10, 13]. Same as the authigenic albite, anal- outcrop of BCF is not known, in this block several deep cime is present as cement and pore-lling material. Ac- drillings reached the BCF, but only the borehole Ib-4 re- cording to mineralogical investigations, amounts of anal- covers sequence of BCF in signicant thickness (between cime range between 8 and 25 wt%. Further mineralogi- 494.2 and 709 m). On the basis of the deep drillings total cal dierence between the two facies is that the BCF in thickness of BCF is estimated to be about 700-900 m in Gorica Block does not contain authigenic K-feldspar, and the perianticlinal structure (WMA) whereas according to dolomite is absent or it is subordinate in the studied sam- our knowledge its thickness is smaller in the Gorica block ples. (about 350 m). The formation has undergone a multistage and com- The BCF sediments are dominantly red and reddish plex diagenetic process from the dissolution of the primary brown in color, reecting the dominantly oxidative envi- evaporite minerals (halite, gypsum, anhydrite) to the for- ronment during sedimentation and early diagenetic pro- mation of authigenic albite and K-feldspar, or calcite- and cesses [2, 6–10]. According to our present-day knowledge albite-bearing pseudomorphs after gypsum and anhydrite. the middle part of BCF has only one reductive interbed- Present-day mineral assemblages and rock types are the ding (greyish black albitic claystone containing pyrite result of these multistage processes. and nely disseminated organic matter), its thickness is In the WMA block six main rock types of BCF can be about 3-4 m. However, several reductive thin layers (green, dened based on mineralogical, geochemical and textu- Clay mineralogy of the Boda Claystone Formation Ë 261 Figure 1: Geological map with depth contour of the top of the Boda Claystone Formation and studied objects after [14] (red circles: studied boreholes: Ib-4, Delta-11). Reddish brown BCF designate the W Mecsek perianticlinal structure.
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